US20090220374A1 - Method and apparatus for using solution precursors for atomic layer deposition - Google Patents

Method and apparatus for using solution precursors for atomic layer deposition Download PDF

Info

Publication number
US20090220374A1
US20090220374A1 US12/396,806 US39680609A US2009220374A1 US 20090220374 A1 US20090220374 A1 US 20090220374A1 US 39680609 A US39680609 A US 39680609A US 2009220374 A1 US2009220374 A1 US 2009220374A1
Authority
US
United States
Prior art keywords
thin film
precursor
vaporized
precursor solution
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/396,806
Inventor
Ce Ma
Qing Min Wang
Patrick J. Helly
Richard Hogle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US12/396,806 priority Critical patent/US20090220374A1/en
Publication of US20090220374A1 publication Critical patent/US20090220374A1/en
Priority to US13/298,574 priority patent/US20120295038A1/en
Priority to US13/298,563 priority patent/US20120294753A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45544Atomic layer deposition [ALD] characterized by the apparatus
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/8305Miscellaneous [e.g., treated surfaces, etc.]

Definitions

  • the present invention relates to new and useful methods and apparatus for delivery of a broader class of precursors for atomic layer deposition.
  • the present invention also relates to atomic layer deposition methods utilizing a new method of delivering precursors.
  • Atomic layer deposition is an enabling technology for next generation conductor barrier layers, high-k gate dielectric layers, high-k capacitance layers, capping layers, and metallic gate electrodes in silicon wafer processes.
  • ALD has also been applied in other electronics industries, such as flat panel display, compound semiconductor, magnetic and optical storage, solar cell, nanotechnology and nanomaterials.
  • ALD is used to build ultra thin and highly conformal layers of metal, oxide, nitride, and others one monolayer at a time in a cyclic deposition process.
  • Oxides and nitrides of many main group metal elements and transition metal elements, such as aluminum, titanium, zirconium, hafnium, and tantalum, have been produced by ALD processes using oxidation or nitridation reactions.
  • Pure metallic layers, such as Ru, Cu, Ta, and others may also be deposited using ALD processes through reduction or combustion reactions.
  • a typical ALD process uses sequential precursor gas pulses to deposit a film one layer at a time.
  • a first precursor gas is introduced into a process chamber and produces a monolayer by reaction at surface of a substrate in the chamber.
  • a second precursor is then introduced to react with the first precursor and form a monolayer of film made up of components of both the first precursor and second precursor, on the substrate.
  • Each pair of pulses (one cycle) produces exactly one monolayer of film allowing for very accurate control of the final film thickness based on the number of deposition cycles performed.
  • high-k materials should have high band gaps and band offsets, high k values, good stability on silicon, minimal SiO 2 interface layer, and high quality interfaces on substrates. Amorphous or high crystalline temperature films are also desirable.
  • Some acceptable high-k dielectric materials are listed in Table 1. Among those listed, HfO 2 , Al 2 O 3 , ZrO 2 , and the related ternary high-k materials have received the most attention for use as gate dielectrics.
  • HfO 2 and ZrO 2 have higher k values but they also have lower break down fields and crystalline temperatures.
  • Y 2 O 3 has high solubility of rare earth materials (e.g. Eu +3 ) and is useful in optical electronics applications.
  • Transition metals and metal nitrides may be used as diffusion barriers to prevent inter-diffusion of metal and silicon in IC devices. These barrier layers are only a few nm in thickness, and are conformal in trenches and vias. Table 2 shows some properties of ALD grown barriers. Desirable properties include low growth temperature ( ⁇ 400° C.) and low film resistivity. For example, Ta/TaN and W/W ⁇ N are preferred as copper diffusion barrier systems. ALD metal thin layers, such as Ru, Cu, Pt, and Ta, have also been deposited for use as barrier and seed layer applications.
  • ALD is an advanced deposition method for high density memory devices when highly conformal and high aspect ratio deposition of high-k dielectric materials and its liners is needed.
  • halides perform well in ALD processes with good self-limiting growth behaviors, but are mostly high melting solids that require high source temperatures.
  • Another disadvantage of using solid precursors is the risk of particle contamination to the substrate.
  • Alkoxides show reduced deposition temperatures in ALD processes, but can decompose in the vapor phase leading to a continuous growth process instead of ALD.
  • ⁇ -diketonates are used in MOCVD processes and are generally more stable towards hydrolysis than alkoxides. However, they are less volatile and require high source and substrate temperatures.
  • a mixed ligand approach with ⁇ -diketonates and alkoxides has been suggested to improve stability of alkoxide MOCVD precursors. Examples are Zr(acac) 2 (hfip) 2 , Zr(O-t-Pr) 2 (thd) 2 .
  • metal nitrate precursors, M(NO 3 ) x , alkylamides, and amidinates show self-limiting growth behavior with very low carbon or halide contamination.
  • the stability of nitrates and amides is an issue in production and many cyclopentadienyls are in solid forms.
  • ALD precursors should have good volatility and be able to saturate the substrate surface quickly through chemisorptions and surface reactions.
  • the ALD half reaction cycles should be completed within 5 seconds, preferably within 1 second.
  • the precursors should be stable within the deposition temperature windows, because un-controllable CVD reactions could occur when the precursor decomposes in gas phase.
  • the precursors themselves should also be highly reactive so that the surface reactions are fast and complete. In addition, complete reactions yield good purity in films.
  • the preferred properties of ALD precursors are given in Table 3.
  • Direct liquid injection methods have been used in many vapor phase deposition processes.
  • U.S. Pat. No. 5,376,409 describes a method of delivering solid precursors that have been dissolved in an appropriate solvent for use in chemical vapor deposition (CVD) techniques.
  • U.S. Pat. No. 5,451,260 describes a method for providing a liquid precursor solution for direct injection using an ultrasonic nozzle for CVD techniques.
  • Beach, et al., in “MOCVD of very thin films of lead lanthanum titanate”, MRS symposium proceedings, 415, 225-30 (1996) set forth a CVD method using multiple precursors dissolved in a single solution.
  • US published patent application 2003/0056728 discloses a pulsed liquid injection method in an atomic vapor deposition (AVD) process, using a precursor in liquid or dissolved form.
  • the liquid dose is too large for ideal ALD operation.
  • Min, et al. “Atomic layer deposition of Al 2 O 3 thin films from a 1-methoxy-2-methyl-2-propoxide complex of aluminum and water”, Chemistry Materials (to be published in 2005), describes a liquid pulsing method for solution precursors, where again the liquid dose is too large for ideal ALD operation.
  • using liquid pulse to achieve monolayer coverage is very difficult, because in an ALD operation, the pulse width of a vapor phase reactant is 1 second or less.
  • the present invention provides unique combinations of solution stabilization and delivery technologies with special ALD operational modes.
  • the present invention allows the use of low-volatility solid ALD precursors dissolved in solvents.
  • the low-volatility solid precursors are often less expensive and often exhibit very high boiling points. Further, unstable solutes can be stabilized in solution and still retain very high boiling points. This is advantageous because the solutions may be delivered at room temperature. After the solution is vaporized, the vapor-phase mixture of precursor and solvent is pulsed into a deposition chamber to assure a true ALD process.
  • the present invention also covers a delivery apparatus that achieves the above result.
  • FIG. 1 is a schematic diagram of an ALD apparatus used to deliver precursors according to one embodiment of the present invention.
  • FIG. 2 is a graph plotting ALD growth of Al 2 O 3 in cycle and time domains according to the present invention.
  • FIG. 3 is a graph plotting ALD growth of HfO 2 in cycle and time domains at three different precursor dosages according to the present invention.
  • FIG. 4 is an XPS spectrum of surface and thin film composition of an ALD grown HfO 2 sample according to the present invention.
  • FIG. 5 is a graph plotting ALD growth of HfO 2 at different temperatures and pulse lengths according to the present invention.
  • FIG. 6 is a graph plotting ALD growth of HfO 2 according to the present invention.
  • FIG. 7 is an XPS spectrum of thin film composition of an ALD grown HfO 2 sample according to the present invention.
  • FIG. 8 is a graph plotting ALD growth of BST in cycle and time domains according to the present invention.
  • FIG. 9 is an XPS spectrum of thin film composition of an ALD grown Ru sample according to the present invention.
  • Stable ALD precursor solutions are prepared in suitable solvents.
  • the precursor solute can be selected from a wide range of low vapor pressure solutes or solids depending upon specific applications. Precursor concentrations are generally maintained from 0.01 M to 1 M, depending upon the liquid flow rate and the vaporization conditions, i.e., pressure and temperature.
  • the precursor solute can be a single molecule or multiple species, wherein the mixture of multiple species is used in making multi-ternary thin films.
  • a major component of the solution is a solvent that does not hinder a normal ALD process. The solvent is chosen so that its boiling point is high enough to ensure no solvent loss in delivery but low enough to ensure total vaporization in a vaporizer.
  • the mixture of the precursor solute in a solvent often will have a higher boiling point than the solvent alone, but the solvent has a high boiling point to prevent any premature separation of solute and solvent during delivery or at the entrance of the vaporizer.
  • Stabilizing additives with concentrations at 0.0001 M to 1 M may be added to the solvent to help prevent premature decomposition of the ALD precursors in the vaporizer.
  • the stabilizing additives provide similar attributes as ligand parts of a precursor and may prolong the shelf-life of the solution.
  • the solution is delivered at room temperature by pumping at pre-selected flow rates. After the solution enters the vaporizer, both solvent and solute are vaporized to form a hot vapor stream. The hot vapor is then switched on and off by a fast action pressure swing mechanism operating at room temperature. This produces normal ALD growth without suffering particle contamination, thermal decomposition or solvent interference.
  • the maximum liquid flow rate or maximum vaporizer pressure can be calculated.
  • the precursor partial pressure when all molecules are in vapor phase should not exceed the material vapor pressure at the given conditions.
  • the selected vaporizer temperature should be below the thermal decomposition temperatures of the precursor and the volume of the vaporizer is selected based on the size of the deposition chamber or substrates being used.
  • Metal or non-metal precursors are selected from those known in the literature and in most cases are readily available commercially at a reasonable cost. Most of these precursors are in solid form, and therefore, are difficult to use directly because of low vapor pressures and high boiling points. In particular, if source temperature is set high to generate enough vapor pressure, the precursor may thermally decompose. In addition, direct use of solid precursors raises the risk of particle contamination or unstable dosage.
  • the precursors according to the present invention include halides, alkoxides, ⁇ -diketonates, nitrates, alkylamides, amidinates, cyclopentadienyls, and other forms of (organic or inorganic) (metal or non-metal) compounds.
  • Typical concentrations of precursors in a solution are from 0.01 M to 1 M, depending upon the liquid flow rate and the vaporization conditions, i.e., pressure and temperature.
  • solutes are given in Table 4, but the present invention is not limited thereto, and any suitable solutes may be used.
  • precursor solutes include Ta(NMe 2 ) 5 and Ta(NMe 2 ) 3 NC 9 H 11 ) that can be used as Tantalum film precursors.
  • solvents are critical to the ALD precursor solutions according to the present invention.
  • the solvents should have reasonable solubility of ALD precursors at room temperature and should be chemically compatible with the precursors.
  • the boiling point of the solvent should be high enough to ensure no solvent loss in delivery and low enough to ensure total vaporization in the vaporizer, although the boiling point of the solvent can be either lower or higher than the precursor solute.
  • the solvent molecules should not compete with precursor molecules for reaction sites on the substrate surface, e.g., the solvent must not be chemically adsorbed on the surface by reacting with a surface hydroxide group.
  • Another example of a solvent useful for the present invention is 2,5-dimethyloxytetrahydrofuran.
  • Stabilizing agents to prevent premature decomposition of ALD precursors in the vaporizer and to prolong the shelf-life of the ALD precursor solutions may also be added.
  • the precursor in solution is normally stable at room temperature with or without the use of stabilizing additives.
  • the liquid solutions can be delivered using a liquid metering pump, a mass flow controller, a syringe pump, a capillary tube, a step pump, a micro-step pump or other suitable equipment at room temperature.
  • the flow rate is controlled from 10 nL/min to 10 mL/min depending upon the size of the deposition systems, i.e. the flow rate can be scaled up as necessary for larger deposition systems.
  • a vaporizer that may have internal or external heating sources or both.
  • the solution can be atomized using a nebulizer, e.g., pneumatic sets or an external energy source, such as inert gas co-axial flow or an ultrasonic source.
  • the vaporizer temperature is controlled by a PID loop and the vaporizer is operated to evaporate both solvent and solute within a given pressure range.
  • the temperature is set at between 100° C. and 350° C. while the pressure is between ⁇ 14 psig and +10 psig.
  • the vaporizer temperature is optimized for specific solute concentration and delivery rate.
  • vaporization temperatures are from 150° C.
  • the hot precursor and solvent vapor may be passed through a particle filter operated at the same or a higher temperature than the vaporizer temperature.
  • the present invention also relates to the delivery of vaporized solution precursors.
  • the first preferred method comprises operating at a constant pumping speed from a vacuum chamber to the exit of the vaporizer.
  • the liquid flow rate must be kept below an established upper limit.
  • a precursor solution of aluminum iso-propoxide has a vapor pressure of about 8 Torr at 140.5° C. If the vaporizer is operated at this temperature, the maximum liquid flow rates for the aluminum iso-propoxide solution at 0.1 M concentration are 48, 242 and 725 microliter/min for pumping speeds of 0.01, 0.05 and 0.15 L/min, respectively.
  • the vaporizer temperature can be increased up to the thermal decomposition temperature of the precursor solute.
  • the second preferred method according to the present invention comprises operating at constant vaporizer pressure. Constant total pressure in the vaporizer can be controlled by pumping speed at the exit of the vaporizer and liquid flow rate at the entrance to the vaporizer. In this method, to achieve the total vaporization of the precursor solution, total vaporizer pressure must be kept below an established upper limit. For example, a precursor solution of aluminum iso-propoxide has a vapor pressure of about 8 Torr at 140.5° C. If the vaporizer is operated at this temperature, the maximum total pressure in the vaporizer for the aluminum iso-propoxide solution at 0.1 M concentration is about 500 Torr when n-Octane is the solvent. To operate at higher total vaporizer pressure for a given precursor solution, the vaporizer temperature can be increased up to the thermal decomposition temperature of the precursor solute.
  • the hot precursor and solvent are switched on and off by a fast action pressure swing device consisting of fast switch valves and an inert gas source.
  • the valves are operated at room temperature and are not exposed to reactive hot vapor.
  • inert gas forms a diffusion barrier to prevent hot vapor from entering the deposition chamber.
  • Inert gas is also sent to the deposition chamber to purge out excess precursor and solvent from the previous cycle which can be then carried to an exhaust system.
  • the valves are on, hot vapor and inert gas enter the deposition chamber to dose deposition on the substrate surface.
  • the ratio of inert gas entering the chamber and going to the exhaust is adjustable by means of metering valves or mass flow controllers.
  • precursor A is on for 0.1 to 10 seconds, followed by a purge for 1 to 10 seconds
  • precursor B is on for 0.1 to 10 seconds, followed by another purge for 1 to 10 seconds.
  • the precursor A could be a metal precursor from the solution vaporizer
  • precursor B could be a gas phase reactant such as water, oxygen, ozone, hydrogen, ammonia, silane, disilane, diborane, hydrogen sulfide, organic amines and hydrazines, or other gaseous molecular or plasma or radical sources.
  • a stop-and-go delivery method may be used instead of a continuous flow method.
  • vaporized precursors may be stored in vessels before delivery into the deposition chamber using a control system including appropriate valves.
  • FIG. 1 An ALD deposition system that can be used in the present invention is shown in FIG. 1 .
  • the system includes solution vessel 10 , for holding the dissolved precursor solution (precursor A), a liquid pump 20 , to pump precursor A to a vaporizer 30 , a vessel 40 , for holding precursor B, such as water, a deposition chamber 50 , having a monitoring device 60 , therein, and an exhaust system 70 .
  • Standard connections and valves may be included as is known in the art to control the method as described above.
  • pulses of the vapor phase precursors from vaporizer 30 and vessel 40 are well separated in time as they enter into the deposition chamber 50 .
  • certain elements, such as the inert gas source are not shown, but are standard in the industry.
  • the ALD system according to the present invention may be used to grow thin films and to operate as a self-limiting ALD process.
  • a silicon wafer substrate is provided in the deposition chamber.
  • the preferred monitoring device is an in-situ device, such as a quartz crystal microbalance (QCM) that monitors the growth of thin films in real time.
  • QCM quartz crystal microbalance
  • the growth surface is a blanket electrode, typically gold that may be modified with oxides, or silicon or other metals for a better nucleation step during the initial ALD growth.
  • the temperature of the deposition chamber is set from 100° C. to 400° C. and is precisely controlled within ⁇ 0.1° C. variation or less using a PID loop.
  • the deposition chamber pressure is set from 0.1 to 10 Torr.
  • the ALD deposition chamber can be coupled to the source and delivery systems.
  • the deposition chamber can be any suitable type, including, but not limited to, flow through reactors, shower head reactors, and spray/injection head reactors.
  • the precursors A and B are carefully separated in the exhaust system to prevent unwanted reactions.
  • Each precursor can be trapped in a foreline trap that may operate at different temperatures.
  • a room temperature trap with stainless steel filter may be used.
  • the separated precursors can be further separated for disposal or recycle.
  • Solid aluminum i-propoxide is dissolved in ethylcyclohexane or other solvents as listed in Table 5.
  • a stabilizing agent such as oxygen containing organic compounds such as THF, 1,4-dioxane, and DMF can be added.
  • the concentration of the aluminum precursor is between 0.1 M and 0.2 M.
  • Liquid flow rate is controlled from 10 mL/min to 10 ⁇ L/min. Water is used as a gas phase reactant.
  • the temperatures of vaporizer and deposition chamber are set at 150° C.-300° C. and 250° C.-400° C., respectively.
  • Typical pulse times for the Al-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively.
  • FIG. 2 shows linear growth of the ALD Al 2 O 3 as a function of cycle number, wherein the Y axis is film thickness in ′ units.
  • the bottom portion of FIG. 2 shows three growth cycles expanded in time domain, where digitized Al solution pulse (A) and water vapor pulse (B) are plotted together with film thickness t(′).
  • Solid [(t-Bu)Cp] 2 HfMe 2 is dissolved in ethylcyclohexane or other solvents as listed in Table 5.
  • a stabilizing agent such as oxygen containing organic compounds such as THF, 1,4-dioxane, DMF, Cp and the like can be added.
  • the Hf precursor concentration is set at from 0.1 M to 0.2 M.
  • Liquid flow rate is controlled at from 10 mL/min to 10 ⁇ L/min. Water is used as a gas phase reactant.
  • the temperatures of vaporizer and deposition chamber are set at 200° C.-300° C. and 200° C.-400° C., respectively.
  • Typical pulse times for the Hf-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively.
  • the upper portion of FIG. 3 shows linear growth of ALD HfO 2 as a function of cycle number, where the Y axis is film thickness in ′ units.
  • the three highlighted graphs show different Hf solution pulse times of 0.5, 1 and 10 seconds respectively, with water vapor pulse and N 2 purge times fixed at 1 and 10 seconds.
  • FIG. 4 shows an HfO 2 film composition using XPS analysis wherein the top portion is surface XPS with environmental carbon contamination and the bottom portion is ALD film composition after 1 minute sputtering. The results indicate there is no impurity incorporation when using the present invention.
  • Self-limited ALD growth is demonstrated in FIG. 5 for each of three different temperature settings where metal precursor pulse length is increased from 0 to 1 seconds to over-saturate the deposition surface.
  • the X-axis is Hf precursor pulse length in seconds and the Y-axis is film QCM growth rate in Angstroms per cycle. As shown, growth rates are independent of precursor dosage after saturation and confirm true ALD deposition. Water vapor pulse length was fixed at 1 second during the test. In this example, 0.2 M[(t-Bu)Cp] 2 HfMe 2 is dissolved in Octane.
  • the XPS data shows the O/Hf ratio to be 2 and carbon impurity below the detection limit of 0.1%.
  • Solid Tetrakis(1-methoxy-2-methyl-2-propoxide)hafnium (IV), Hf (mmp) 4 is dissolved in ethylcyclohexane or other solvents as listed in Table 5.
  • a stabilizing agent such as oxygen containing organic compounds such as THF, 1,4-dioxane, DMF, Cp and the like can be added.
  • the Hf precursor concentration is set at 0.1 M to 0.2 M.
  • Liquid flow rate is controlled from 10 mL/min to 10 ⁇ L/min. Water is used as a gas phase reactant.
  • the temperatures of vaporizer and deposition chamber are set at 150° C.-300° C. and 200° C.-350° C., respectively.
  • Typical pulse times for the Hf-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively.
  • FIG. 6 shows linear growth of ALD HfO 2 as a function of cycle number, where the Y axis is film thickness in Angstroms.
  • FIG. 7 shows the HfO 2 film composition as formed in this Example, using XPS analysis after two minutes sputtering to remove surface contamination. The results indicate there is no impurity incorporation when using the present invention.
  • the XPS data shows the O/Hf ratio to be 2.3 and carbon impurity below the detection limit of 0.1%.
  • Solids of Ba(O-iPr) 2 , Sr(O-iPr) 2 , and Ti(O-iPr) 4 are dissolved in ethylcyclohexane or other solvents as listed in Table 5 with different mixing ratios.
  • Stabilizing agents such as oxygen containing organic compounds such as THF, 1,4-dioxane, and DMF can be added.
  • the BST precursor concentration is set at 0.1 M to 0.2 M for each component.
  • Liquid flow rate is controlled from 10 mL/min to 10 ⁇ L/min. Water is used as a gas phase reactant.
  • the temperatures of vaporizer and deposition chamber are set at 200° C.-350° C. and 300° C.-400° C., respectively.
  • Typical pulse times for the mix-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10 and 1-10 seconds, respectively.
  • the upper portion of FIG. 8 shows linear growth of ALD BST as a function of cycle number, where the Y axis is film thickness in ′ units.
  • the bottom portion of FIG. 8 shows four and a half growth cycles expanded in time domain with digitized BST solution pulse and water vapor pulse plotted together with film thickness t(′).
  • Solid RuCp 2 is dissolved in dioxane, dioxane/octane or 2,5-dimethyloxytetrahydrofuran/octane.
  • concentration of Ru precursor is set at 0.05 M to 0.2 M.
  • a stabilizing agents such as Cp and the like can be added.
  • Liquid flow rate is controlled from 10 mL/min to 10 ⁇ L/min.
  • Oxygen gas is used as a combustion agent.
  • the temperatures of vaporizer and deposition chamber are set at 140° C.-300° C. and 300° C.-400° C., respectively.
  • Typical pulse times for the Ru-solution, purge, oxygen, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively.
  • FIG. 9 shows Ru film composition using XPS analysis after 1.5 minutes sputtering to remove surface contamination. The results indicate there is no impurity incorporation when using the present invention.
  • the film resistivity is about 12 micro-Ohm

Abstract

A unique combination of solution stabilization and delivery technologies with special ALD operation is provided. A wide range of low volatility solid ALD precursors dissolved in solvents are used. Unstable solutes may be stabilized in solution and all of the solutions may be delivered at room temperature. After the solutions are vaporized, the vapor phase precursors and solvents are pulsed into a deposition chamber to assure true ALD film growth.

Description

    FIELD OF THE INVENTION
  • The present invention relates to new and useful methods and apparatus for delivery of a broader class of precursors for atomic layer deposition. The present invention also relates to atomic layer deposition methods utilizing a new method of delivering precursors.
  • BACKGROUND OF THE INVENTION
  • Atomic layer deposition (ALD) is an enabling technology for next generation conductor barrier layers, high-k gate dielectric layers, high-k capacitance layers, capping layers, and metallic gate electrodes in silicon wafer processes. ALD has also been applied in other electronics industries, such as flat panel display, compound semiconductor, magnetic and optical storage, solar cell, nanotechnology and nanomaterials. ALD is used to build ultra thin and highly conformal layers of metal, oxide, nitride, and others one monolayer at a time in a cyclic deposition process. Oxides and nitrides of many main group metal elements and transition metal elements, such as aluminum, titanium, zirconium, hafnium, and tantalum, have been produced by ALD processes using oxidation or nitridation reactions. Pure metallic layers, such as Ru, Cu, Ta, and others may also be deposited using ALD processes through reduction or combustion reactions.
  • A typical ALD process uses sequential precursor gas pulses to deposit a film one layer at a time. In particular, a first precursor gas is introduced into a process chamber and produces a monolayer by reaction at surface of a substrate in the chamber. A second precursor is then introduced to react with the first precursor and form a monolayer of film made up of components of both the first precursor and second precursor, on the substrate. Each pair of pulses (one cycle) produces exactly one monolayer of film allowing for very accurate control of the final film thickness based on the number of deposition cycles performed.
  • As semiconductor devices continue to get more densely packed with devices, channel lengths also have to be made smaller and smaller. For future electronic device technologies, it will be necessary to replace SiO2 and SiON gate dielectrics with ultra thin high-k oxides having effective oxide thickness (EOT) less than 1.5 nm. Preferably, high-k materials should have high band gaps and band offsets, high k values, good stability on silicon, minimal SiO2 interface layer, and high quality interfaces on substrates. Amorphous or high crystalline temperature films are also desirable. Some acceptable high-k dielectric materials are listed in Table 1. Among those listed, HfO2, Al2O3, ZrO2, and the related ternary high-k materials have received the most attention for use as gate dielectrics. HfO2 and ZrO2 have higher k values but they also have lower break down fields and crystalline temperatures. The aluminates of Hf and Zr possess the combined benefits of higher k values and higher break down fields. Y2O3 has high solubility of rare earth materials (e.g. Eu+3) and is useful in optical electronics applications.
  • TABLE 1
    Dielectric properties of ALD high-k gate materials
    EOT (@ 5 Break down Field EBD Crystalline
    Material K nm film) (MV/cm @ 1 μA/cm2) Temp (° C.)
    HfO2 13-17 1.3 1-5 400-600
    Al2O3 7-9 2.44 3-8  900-1000
    ZrO 2 20 0.98 1  <300 *
    HfxAlyOz  8-20 1.22 N/A 900
    ZrxAlyOz  8-20 1.22 N/A 975
    Y2O3 12-15 1.44 4 <600 
    Ta2O5 23-25 0.81 0.5-1.5 500-700
    NbxAlyOz  8 2.44 5 N/A
    HfxSiyOz N/A N/A N/A 800
    TaxTiyOz 27-28 0.71 1 N/A
    Al2O3/HfO2 N/A N/A N/A N/A
    Al2O3/TiO2  9-18 1.44 5-7 N/A
    * as a function of film thickness
  • Transition metals and metal nitrides may be used as diffusion barriers to prevent inter-diffusion of metal and silicon in IC devices. These barrier layers are only a few nm in thickness, and are conformal in trenches and vias. Table 2 shows some properties of ALD grown barriers. Desirable properties include low growth temperature (<400° C.) and low film resistivity. For example, Ta/TaN and W/W×N are preferred as copper diffusion barrier systems. ALD metal thin layers, such as Ru, Cu, Pt, and Ta, have also been deposited for use as barrier and seed layer applications.
  • TABLE 2
    Film properties of ALD nitride barrier layer materials
    Metal Other Growth Temp Resistivity
    Film precursor precursors (° C.) (μΩ*cm)
    TaN TaCl5 Zn + NH3 400-500 900
    TaN TaCl5 H/N plasma 300-400 300-400
    TaN(C) TBTDET NH3 250 N/A
    TaN(C) TBTDET H plasma N/A 250
    TaNx TaF5 H/N plasma 250 104-103
    Ta3N5 TaCl5 NH3 400-500 105-104
    W2N WF6 NH3 330-530 4500
    TiN TiCl4 NH3 500 250
    TiN TiCl4 Zn + NH3 500 50
    TiN TiI4 NH3 400-500 380-70 
    TiN TiCl4 Me2NNH2 350 500
    TiN TEMAT NH3 160-320 600 (post
    annealed)
    TiN Ti(NMe2)4 NH3 180 5000
  • ALD is an advanced deposition method for high density memory devices when highly conformal and high aspect ratio deposition of high-k dielectric materials and its liners is needed. High-k oxides listed in Table 1, such as Al2O3, as well as ferroelectric materials, such as BST, PZT, and SBT layers, have been used as capacitor dielectrics in memory devices.
  • Several types of traditional vapor phase deposition precursors have been tested in ALD processes, including halides, alkoxides, β-diketonates, and newer alkylamides and cyclopentadienyls materials. Halides perform well in ALD processes with good self-limiting growth behaviors, but are mostly high melting solids that require high source temperatures. Another disadvantage of using solid precursors is the risk of particle contamination to the substrate. In addition, there is an issue of instability in flux or dosage associated with the solid precursors. Alkoxides show reduced deposition temperatures in ALD processes, but can decompose in the vapor phase leading to a continuous growth process instead of ALD. β-diketonates are used in MOCVD processes and are generally more stable towards hydrolysis than alkoxides. However, they are less volatile and require high source and substrate temperatures. A mixed ligand approach with β-diketonates and alkoxides has been suggested to improve stability of alkoxide MOCVD precursors. Examples are Zr(acac)2(hfip)2, Zr(O-t-Pr)2(thd)2. In addition, metal nitrate precursors, M(NO3)x, alkylamides, and amidinates, show self-limiting growth behavior with very low carbon or halide contamination. However, the stability of nitrates and amides is an issue in production and many cyclopentadienyls are in solid forms.
  • In general, ALD precursors should have good volatility and be able to saturate the substrate surface quickly through chemisorptions and surface reactions. The ALD half reaction cycles should be completed within 5 seconds, preferably within 1 second. The exposure dosage should be below 108 Laugmuir (1 Torr*sec=106 Laugmuir). The precursors should be stable within the deposition temperature windows, because un-controllable CVD reactions could occur when the precursor decomposes in gas phase. The precursors themselves should also be highly reactive so that the surface reactions are fast and complete. In addition, complete reactions yield good purity in films. The preferred properties of ALD precursors are given in Table 3.
  • TABLE 3
    Preferred ALD precursor properties
    Requirement
    Class Property Range
    Primary Good volatility >0.1 Torr
    Primary Liquid or gas At room temperatures
    Primary Good thermal stability >250° C. or >350° C. in
    gas phase
    Primary Fast saturation <5 sec or <1 sec
    Primary Highly reactive Complete surface reactive cycles
    Primary Non reactive volatile No product and reagent reaction
    byproduct
    Secondary High growth rate Up to a monolayer a cycle
    Secondary Less shield effect Free up un-occupied sites
    from ligands
    Secondary Cost and purity Key impurity: H2O, O2
    Secondary Shelf-life >1-2 years
    Secondary Halides Free in films
    Secondary Carbon <1% in non carbon containing
    films
  • Because of stringent requirements for ALD precursors as noted in Table 3, new types of ALD precursors are needed that are more stable, exhibit higher volatility, and are better suited for ALD. However, the cost of developing new precursors is a significant obstacle. In this light, the prior art related to chemical vapor deposition (CVD) processes provides some useful background information.
  • Direct liquid injection methods have been used in many vapor phase deposition processes. For example, U.S. Pat. No. 5,376,409 describes a method of delivering solid precursors that have been dissolved in an appropriate solvent for use in chemical vapor deposition (CVD) techniques. U.S. Pat. No. 5,451,260 describes a method for providing a liquid precursor solution for direct injection using an ultrasonic nozzle for CVD techniques. Beach, et al., in “MOCVD of very thin films of lead lanthanum titanate”, MRS symposium proceedings, 415, 225-30 (1996) set forth a CVD method using multiple precursors dissolved in a single solution. Choi, et al., “Structure stability of metallorganic chemical vapor deposited (Ba, Sr)RuO3 electrodes for integration of high dielectric constant thin films”, Journal of the Electrochemical Society, 149(4), G232-5 (2002), describes a CVD method using liquid injection of a multiple component solution. Zhao, et al., “Metallorganic CVD of high-quality PZT thin films at low temperature with new Zr and Ti precursors having mmp ligands”, Journal of the Electrochemical Society, 151(5), C283-91 (2004) discusses another CVD method using a multiple precursor solution liquid delivery system. As noted, each of these references discuss CVD techniques and are interesting only for the discussion of various precursor materials, including solid precursors dissolved in appropriate solvents.
  • There is also some prior art background material relating to ALD processes. Cho, et al., “Atomic layer deposition (ALD) of Bismuth Titanium oxide thin films using direct liquid injection (DLI) method”, Integrated Ferroelectrics, 59, 1483-9, (2003), reports on the use of solid precursors dissolved in a solvent. However, no information is provided concerning the delivery and deposition methods.
  • US published patent application 2003/0056728 discloses a pulsed liquid injection method in an atomic vapor deposition (AVD) process, using a precursor in liquid or dissolved form. The liquid dose is too large for ideal ALD operation. Min, et al., “Atomic layer deposition of Al2O3 thin films from a 1-methoxy-2-methyl-2-propoxide complex of aluminum and water”, Chemistry Materials (to be published in 2005), describes a liquid pulsing method for solution precursors, where again the liquid dose is too large for ideal ALD operation. In fact, using liquid pulse to achieve monolayer coverage is very difficult, because in an ALD operation, the pulse width of a vapor phase reactant is 1 second or less. One issue is that the shape of a vaporized liquid pulse is distorted in time space and sharp leading and tailing edges of the liquid pulse can be lost after vaporization. It is therefore difficult to synchronize two well separated reactants to perform self-limiting and sequential ALD growth. The liquid pulse methods described in the two references above do not represent true ALD processes but rather variants of CVD processes.
  • US published patent application 2004/0079286, describes a two-phase delivery system for ALD wherein both vapor and liquid phase coexist in a vaporizer after liquid injection. This process will not work for solution based precursors or multi-component mixtures where material separation would occur.
  • There remains a need in the art for improvements to ALD precursors and methods of using such precursors in ALD processes.
  • SUMMARY OF INVENTION
  • The present invention provides unique combinations of solution stabilization and delivery technologies with special ALD operational modes. In particular, the present invention allows the use of low-volatility solid ALD precursors dissolved in solvents. The low-volatility solid precursors are often less expensive and often exhibit very high boiling points. Further, unstable solutes can be stabilized in solution and still retain very high boiling points. This is advantageous because the solutions may be delivered at room temperature. After the solution is vaporized, the vapor-phase mixture of precursor and solvent is pulsed into a deposition chamber to assure a true ALD process. The present invention also covers a delivery apparatus that achieves the above result.
  • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a schematic diagram of an ALD apparatus used to deliver precursors according to one embodiment of the present invention.
  • FIG. 2 is a graph plotting ALD growth of Al2O3 in cycle and time domains according to the present invention.
  • FIG. 3 is a graph plotting ALD growth of HfO2 in cycle and time domains at three different precursor dosages according to the present invention.
  • FIG. 4 is an XPS spectrum of surface and thin film composition of an ALD grown HfO2 sample according to the present invention.
  • FIG. 5 is a graph plotting ALD growth of HfO2 at different temperatures and pulse lengths according to the present invention.
  • FIG. 6 is a graph plotting ALD growth of HfO2 according to the present invention.
  • FIG. 7 is an XPS spectrum of thin film composition of an ALD grown HfO2 sample according to the present invention.
  • FIG. 8 is a graph plotting ALD growth of BST in cycle and time domains according to the present invention.
  • FIG. 9 is an XPS spectrum of thin film composition of an ALD grown Ru sample according to the present invention.
  • DETAILED DESCRIPTION OF THE INVENTION
  • Stable ALD precursor solutions are prepared in suitable solvents. The precursor solute can be selected from a wide range of low vapor pressure solutes or solids depending upon specific applications. Precursor concentrations are generally maintained from 0.01 M to 1 M, depending upon the liquid flow rate and the vaporization conditions, i.e., pressure and temperature. The precursor solute can be a single molecule or multiple species, wherein the mixture of multiple species is used in making multi-ternary thin films. A major component of the solution is a solvent that does not hinder a normal ALD process. The solvent is chosen so that its boiling point is high enough to ensure no solvent loss in delivery but low enough to ensure total vaporization in a vaporizer. The mixture of the precursor solute in a solvent often will have a higher boiling point than the solvent alone, but the solvent has a high boiling point to prevent any premature separation of solute and solvent during delivery or at the entrance of the vaporizer. Stabilizing additives with concentrations at 0.0001 M to 1 M may be added to the solvent to help prevent premature decomposition of the ALD precursors in the vaporizer. In addition, the stabilizing additives provide similar attributes as ligand parts of a precursor and may prolong the shelf-life of the solution. The solution is delivered at room temperature by pumping at pre-selected flow rates. After the solution enters the vaporizer, both solvent and solute are vaporized to form a hot vapor stream. The hot vapor is then switched on and off by a fast action pressure swing mechanism operating at room temperature. This produces normal ALD growth without suffering particle contamination, thermal decomposition or solvent interference.
  • In accordance with the present invention, at a given temperature and precursor concentration, the maximum liquid flow rate or maximum vaporizer pressure can be calculated. In particular, to produce a single vapor phase solution precursor, the precursor partial pressure when all molecules are in vapor phase should not exceed the material vapor pressure at the given conditions. The selected vaporizer temperature should be below the thermal decomposition temperatures of the precursor and the volume of the vaporizer is selected based on the size of the deposition chamber or substrates being used.
  • Metal or non-metal precursors are selected from those known in the literature and in most cases are readily available commercially at a reasonable cost. Most of these precursors are in solid form, and therefore, are difficult to use directly because of low vapor pressures and high boiling points. In particular, if source temperature is set high to generate enough vapor pressure, the precursor may thermally decompose. In addition, direct use of solid precursors raises the risk of particle contamination or unstable dosage. The precursors according to the present invention include halides, alkoxides, β-diketonates, nitrates, alkylamides, amidinates, cyclopentadienyls, and other forms of (organic or inorganic) (metal or non-metal) compounds. Typical concentrations of precursors in a solution are from 0.01 M to 1 M, depending upon the liquid flow rate and the vaporization conditions, i.e., pressure and temperature. Examples of solutes are given in Table 4, but the present invention is not limited thereto, and any suitable solutes may be used.
  • TABLE 4
    Examples of ALD precursor solutes
    bp (° C./
    Name Formula MW Mp (° C.) mmHg) Density (g/mL)
    Tetrakis(ethylmethylamino)hafnium Hf[N(EtMe)]4 410.9 −50   79/0.1 1.324
    (TEMAH)
    Hafnuim (IV) Nitrate, Hf(NO3)4 426.51 >300 n/a
    anhydrous
    Hafnuim (IV) Iodide, HfI4 686.11 400 n/a 5.6
    anhydrous (subl.)
    Dimethylbis(t-butyl [(t-Bu)Cp]2HfMe2 450.96 73-76 n/a
    cyclopentadienyl hafnium (IV)
    Tetrakis(1-methoxy-2-methyl- Hf(O2C5H11)4 591 n/a   135/0.01
    2-propoxide) hafnium (IV)
    Di(cyclopentadienyl)Hf Cp2HfCl2 379.58 230-233 n/a
    dichloride
    Hafnium tert-butoxide Hf(OC4H9)4 470.94 n/a 90/5
    Hafnium ethoxide Hf(OC2H5)4 358.73 178-180 180-200/13   
    Aluminum i-propoxide Al(OC3H7)3 204.25 118.5 140.5/8   1.0346
    Lead t-butoxide Pb(OC(CH3)3)2 353.43
    Zirconium (IV) t-butoxide Zr(OC(CH3)3)4 383.68 90/5; 81/3 0.985
    Titanium (IV) i-propoxide Ti(OCH(CH3)2)4 284.25 20 58/1 0.955
    Barium i-propoxide Ba(OC3H7)2 255.52 200 (dec) n/a
    Strontium i-propoxide Sr(OC3H7)2 205.8
    Bis(pentamethylCp) Barium Ba(C5Me5)2 409.8
    Bis(tripropylCp) Strontium Sr(C5i-Pr3H2)2 472.3
    (Trimethyl)pentamethylcyclopentadienyl Ti(C5Me5)(Me3) 228.22
    titanium (IV)
    Bis(2,2,6,6-tetramethyl-3,5-heptanedionato) Ba(thd)2 * 503.85 88
    barium triglyme triglyme (682.08)
    adduct
    Bis(2,2,6,6-tetramethyl-3,5-heptanedionato) Sr(thd)2 * 454.16 75
    strontium triglyme (632.39)
    triglyme adduct
    Tris(2,2,6,6-tetramethyl-3,5-heptanedionato) Ti(thd)3 597.7 75/0.1 (sp)
    titanium(III)
    Bis(cyclpentadinyl)Ruthenium RuCp2 231.26 200 80-85/0.01
    (II)
  • Other examples of precursor solutes include Ta(NMe2)5 and Ta(NMe2)3NC9H11) that can be used as Tantalum film precursors.
  • The selection of solvents is critical to the ALD precursor solutions according to the present invention. In particular, the solvents should have reasonable solubility of ALD precursors at room temperature and should be chemically compatible with the precursors. The boiling point of the solvent should be high enough to ensure no solvent loss in delivery and low enough to ensure total vaporization in the vaporizer, although the boiling point of the solvent can be either lower or higher than the precursor solute. The solvent molecules should not compete with precursor molecules for reaction sites on the substrate surface, e.g., the solvent must not be chemically adsorbed on the surface by reacting with a surface hydroxide group. The solvent molecules or their fragments should not be any part of the ALD solid film composition. Examples of solvents useful in the present invention are given in Table 5, but are not limited thereto, as any suitable solvent meeting the above criteria may be used.
  • TABLE 5
    Examples of solvents
    BP@760
    Name Formula Torr (° C.)
    Dioxane C4H8O2 101
    Toluene C7H8 110.6
    n-butyl acetate CH3CO2(n-Bu) 124-126
    Octane C8H18 125-127
    Ethylcyclohexane C8H16 132
    2-Methoxyethyl acetate CH3CO2(CH2)2OCH3 145
    Cyclohexanone C6H10O 155
    Propylcyclohexane C9H18 156
    2-Methoxyethyl Ether (diglyme) (CH3OCH2CH2)2O 162
    Butylcyclohexane C10H20 178
  • Another example of a solvent useful for the present invention is 2,5-dimethyloxytetrahydrofuran.
  • Stabilizing agents to prevent premature decomposition of ALD precursors in the vaporizer and to prolong the shelf-life of the ALD precursor solutions may also be added. However, the precursor in solution is normally stable at room temperature with or without the use of stabilizing additives. Once the solid precursor has been dissolved in the solvent, the liquid solutions can be delivered using a liquid metering pump, a mass flow controller, a syringe pump, a capillary tube, a step pump, a micro-step pump or other suitable equipment at room temperature. The flow rate is controlled from 10 nL/min to 10 mL/min depending upon the size of the deposition systems, i.e. the flow rate can be scaled up as necessary for larger deposition systems.
  • One method according to the present invention is described as follows. Precisely controlled liquid solution is injected into a vaporizer that may have internal or external heating sources or both. Optionally, the solution can be atomized using a nebulizer, e.g., pneumatic sets or an external energy source, such as inert gas co-axial flow or an ultrasonic source. The vaporizer temperature is controlled by a PID loop and the vaporizer is operated to evaporate both solvent and solute within a given pressure range. In general, the temperature is set at between 100° C. and 350° C. while the pressure is between −14 psig and +10 psig. The vaporizer temperature is optimized for specific solute concentration and delivery rate. Preferably, vaporization temperatures are from 150° C. to 250° C. and flow rates are between 0.1 μL/min and 100 μL/min. If the temperature is too low, precursor molecules may condense because of low saturation partial pressure and if the temperature is too high, the precursor molecules may decompose inside the vaporizer chamber. To ensure particle-free vapor phase formation before ALD, the hot precursor and solvent vapor may be passed through a particle filter operated at the same or a higher temperature than the vaporizer temperature.
  • The present invention also relates to the delivery of vaporized solution precursors. There are two preferred delivery methods for the vaporized solution precursors according to the present invention. The first preferred method comprises operating at a constant pumping speed from a vacuum chamber to the exit of the vaporizer. In this method, to achieve the total vaporization of the precursor solution, the liquid flow rate must be kept below an established upper limit. For example, a precursor solution of aluminum iso-propoxide has a vapor pressure of about 8 Torr at 140.5° C. If the vaporizer is operated at this temperature, the maximum liquid flow rates for the aluminum iso-propoxide solution at 0.1 M concentration are 48, 242 and 725 microliter/min for pumping speeds of 0.01, 0.05 and 0.15 L/min, respectively. To deliver higher liquid flow rates of a given precursor solution, the vaporizer temperature can be increased up to the thermal decomposition temperature of the precursor solute.
  • The second preferred method according to the present invention comprises operating at constant vaporizer pressure. Constant total pressure in the vaporizer can be controlled by pumping speed at the exit of the vaporizer and liquid flow rate at the entrance to the vaporizer. In this method, to achieve the total vaporization of the precursor solution, total vaporizer pressure must be kept below an established upper limit. For example, a precursor solution of aluminum iso-propoxide has a vapor pressure of about 8 Torr at 140.5° C. If the vaporizer is operated at this temperature, the maximum total pressure in the vaporizer for the aluminum iso-propoxide solution at 0.1 M concentration is about 500 Torr when n-Octane is the solvent. To operate at higher total vaporizer pressure for a given precursor solution, the vaporizer temperature can be increased up to the thermal decomposition temperature of the precursor solute.
  • To deposit the ALD layers, the hot precursor and solvent are switched on and off by a fast action pressure swing device consisting of fast switch valves and an inert gas source. The valves are operated at room temperature and are not exposed to reactive hot vapor. When valves are switched off, inert gas forms a diffusion barrier to prevent hot vapor from entering the deposition chamber. Inert gas is also sent to the deposition chamber to purge out excess precursor and solvent from the previous cycle which can be then carried to an exhaust system. When the valves are on, hot vapor and inert gas enter the deposition chamber to dose deposition on the substrate surface. The ratio of inert gas entering the chamber and going to the exhaust is adjustable by means of metering valves or mass flow controllers. Typically, precursor A is on for 0.1 to 10 seconds, followed by a purge for 1 to 10 seconds, precursor B is on for 0.1 to 10 seconds, followed by another purge for 1 to 10 seconds. In such an operation, the precursor A could be a metal precursor from the solution vaporizer, and precursor B could be a gas phase reactant such as water, oxygen, ozone, hydrogen, ammonia, silane, disilane, diborane, hydrogen sulfide, organic amines and hydrazines, or other gaseous molecular or plasma or radical sources. In another embodiment, a stop-and-go delivery method may be used instead of a continuous flow method. In addition, vaporized precursors may be stored in vessels before delivery into the deposition chamber using a control system including appropriate valves.
  • An ALD deposition system that can be used in the present invention is shown in FIG. 1. In particular, the system includes solution vessel 10, for holding the dissolved precursor solution (precursor A), a liquid pump 20, to pump precursor A to a vaporizer 30, a vessel 40, for holding precursor B, such as water, a deposition chamber 50, having a monitoring device 60, therein, and an exhaust system 70. Standard connections and valves may be included as is known in the art to control the method as described above. By using the system shown in FIG. 1, pulses of the vapor phase precursors from vaporizer 30 and vessel 40 are well separated in time as they enter into the deposition chamber 50. Further, certain elements, such as the inert gas source are not shown, but are standard in the industry.
  • The ALD system according to the present invention may be used to grow thin films and to operate as a self-limiting ALD process. In operation, a silicon wafer substrate is provided in the deposition chamber. The preferred monitoring device is an in-situ device, such as a quartz crystal microbalance (QCM) that monitors the growth of thin films in real time. For example, a QCM with starting frequency at 6 MHz installed in a tubular reactor may be used. The growth surface is a blanket electrode, typically gold that may be modified with oxides, or silicon or other metals for a better nucleation step during the initial ALD growth. The temperature of the deposition chamber is set from 100° C. to 400° C. and is precisely controlled within ±0.1° C. variation or less using a PID loop. The deposition chamber pressure is set from 0.1 to 10 Torr. For more continuous production, the ALD deposition chamber can be coupled to the source and delivery systems. The deposition chamber can be any suitable type, including, but not limited to, flow through reactors, shower head reactors, and spray/injection head reactors.
  • The precursors A and B are carefully separated in the exhaust system to prevent unwanted reactions. Each precursor can be trapped in a foreline trap that may operate at different temperatures. For example, a room temperature trap with stainless steel filter may be used. The separated precursors can be further separated for disposal or recycle.
  • Several examples of the use of solid precursors dissolved in a solvent and used in an ALD process according to the present invention are provided below.
  • EXAMPLE 1 Al2O3 Thin Film
  • Solid aluminum i-propoxide is dissolved in ethylcyclohexane or other solvents as listed in Table 5. A stabilizing agent, such as oxygen containing organic compounds such as THF, 1,4-dioxane, and DMF can be added. The concentration of the aluminum precursor is between 0.1 M and 0.2 M. Liquid flow rate is controlled from 10 mL/min to 10 μL/min. Water is used as a gas phase reactant. The temperatures of vaporizer and deposition chamber are set at 150° C.-300° C. and 250° C.-400° C., respectively. Typical pulse times for the Al-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively. The upper portion of FIG. 2 shows linear growth of the ALD Al2O3 as a function of cycle number, wherein the Y axis is film thickness in ′ units. The bottom portion of FIG. 2 shows three growth cycles expanded in time domain, where digitized Al solution pulse (A) and water vapor pulse (B) are plotted together with film thickness t(′).
  • EXAMPLE 2 HfO2 Thin Film
  • Solid [(t-Bu)Cp]2HfMe2 is dissolved in ethylcyclohexane or other solvents as listed in Table 5. A stabilizing agent, such as oxygen containing organic compounds such as THF, 1,4-dioxane, DMF, Cp and the like can be added. The Hf precursor concentration is set at from 0.1 M to 0.2 M. Liquid flow rate is controlled at from 10 mL/min to 10 μL/min. Water is used as a gas phase reactant. The temperatures of vaporizer and deposition chamber are set at 200° C.-300° C. and 200° C.-400° C., respectively. Typical pulse times for the Hf-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively. The upper portion of FIG. 3 shows linear growth of ALD HfO2 as a function of cycle number, where the Y axis is film thickness in ′ units. The three highlighted graphs show different Hf solution pulse times of 0.5, 1 and 10 seconds respectively, with water vapor pulse and N2 purge times fixed at 1 and 10 seconds. FIG. 4 shows an HfO2 film composition using XPS analysis wherein the top portion is surface XPS with environmental carbon contamination and the bottom portion is ALD film composition after 1 minute sputtering. The results indicate there is no impurity incorporation when using the present invention.
  • EXAMPLE 3 Self-Limited HfO2 Thin Film
  • Self-limited ALD growth is demonstrated in FIG. 5 for each of three different temperature settings where metal precursor pulse length is increased from 0 to 1 seconds to over-saturate the deposition surface. The X-axis is Hf precursor pulse length in seconds and the Y-axis is film QCM growth rate in Angstroms per cycle. As shown, growth rates are independent of precursor dosage after saturation and confirm true ALD deposition. Water vapor pulse length was fixed at 1 second during the test. In this example, 0.2 M[(t-Bu)Cp]2HfMe2 is dissolved in Octane. The XPS data shows the O/Hf ratio to be 2 and carbon impurity below the detection limit of 0.1%.
  • EXAMPLE 3 HfO2 Thin Film
  • Solid Tetrakis(1-methoxy-2-methyl-2-propoxide)hafnium (IV), Hf(mmp)4 is dissolved in ethylcyclohexane or other solvents as listed in Table 5. A stabilizing agent, such as oxygen containing organic compounds such as THF, 1,4-dioxane, DMF, Cp and the like can be added. The Hf precursor concentration is set at 0.1 M to 0.2 M. Liquid flow rate is controlled from 10 mL/min to 10 μL/min. Water is used as a gas phase reactant. The temperatures of vaporizer and deposition chamber are set at 150° C.-300° C. and 200° C.-350° C., respectively. Typical pulse times for the Hf-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively. FIG. 6 shows linear growth of ALD HfO2 as a function of cycle number, where the Y axis is film thickness in Angstroms. FIG. 7 shows the HfO2 film composition as formed in this Example, using XPS analysis after two minutes sputtering to remove surface contamination. The results indicate there is no impurity incorporation when using the present invention. The XPS data shows the O/Hf ratio to be 2.3 and carbon impurity below the detection limit of 0.1%.
  • EXAMPLE 4 BST Thin Films
  • Solids of Ba(O-iPr)2, Sr(O-iPr)2, and Ti(O-iPr)4 are dissolved in ethylcyclohexane or other solvents as listed in Table 5 with different mixing ratios. Stabilizing agents such as oxygen containing organic compounds such as THF, 1,4-dioxane, and DMF can be added. The BST precursor concentration is set at 0.1 M to 0.2 M for each component. Liquid flow rate is controlled from 10 mL/min to 10 μL/min. Water is used as a gas phase reactant. The temperatures of vaporizer and deposition chamber are set at 200° C.-350° C. and 300° C.-400° C., respectively. Typical pulse times for the mix-solution, purge, water, and purge steps are 0.1-10, 1-10, 0.1-10 and 1-10 seconds, respectively. The upper portion of FIG. 8 shows linear growth of ALD BST as a function of cycle number, where the Y axis is film thickness in ′ units. The bottom portion of FIG. 8 shows four and a half growth cycles expanded in time domain with digitized BST solution pulse and water vapor pulse plotted together with film thickness t(′).
  • EXAMPLE 5 Ru Thin Film
  • Solid RuCp2 is dissolved in dioxane, dioxane/octane or 2,5-dimethyloxytetrahydrofuran/octane. The concentration of Ru precursor is set at 0.05 M to 0.2 M. A stabilizing agents such as Cp and the like can be added. Liquid flow rate is controlled from 10 mL/min to 10 μL/min. Oxygen gas is used as a combustion agent. The temperatures of vaporizer and deposition chamber are set at 140° C.-300° C. and 300° C.-400° C., respectively. Typical pulse times for the Ru-solution, purge, oxygen, and purge steps are 0.1-10, 1-10, 0.1-10, and 1-10 seconds, respectively. FIG. 9 shows Ru film composition using XPS analysis after 1.5 minutes sputtering to remove surface contamination. The results indicate there is no impurity incorporation when using the present invention. The film resistivity is about 12 micro-Ohm*cm by 4-point probe measurement.
  • It is anticipated that other embodiments and variations of the present invention will become readily apparent to the skilled artisan in the light of the foregoing description, and it is intended that such embodiments and variations likewise be included within the scope of the invention as set out in the appended claims.

Claims (45)

1. A method of atomic layer deposition comprising:
alternately delivering a vaporized precursor solution and a vaporized reaction solution to a deposition chamber;
forming a monolayer of components of the precursor solution and reaction solution on surface of a substrate in the deposition chamber; and
repeating until a thin film of a predetermined thickness is formed;
wherein the vaporized precursor solution comprises one or more low volatility precursors dissolved in a solvent; and
wherein the precursor solution is delivered to a vaporizer at room temperature and vaporized without decomposition or condensation by operating a vacuum pump associated with the vaporizer at constant pumping speed.
2. A method according to claim 1, wherein the precursor is a solid.
3. A method according to claim 1, wherein the precursor is selected from the group consisting of halides, alkoxides, β-diketonates, nitrates, alkylamides, amidinates, cyclopentadienyls, and other forms of organic or inorganic metal or non-metal compounds.
4. A method according to claim 3, wherein the precursor is selected from the group consisting of Hf[N(EtMe)]4, Hf(NO3)4, HfCl4, HfI4, [(t-Bu)Cp]2HfMe2, Hf(O2C5H11)4, Cp2HfCl2, Hf(OC4H9)4, Hf(OC2H5)4, Al(OC3H7)3, Pb(OC(CH3)3)2, Z,r(OC(CH3)3)4, Ti(OCH(CH3)2)4, Ba(OC3H7)2, Sr(OC3H7)2, Ba(C5Me5)2, Sr(C5i-Pr3H2)2, Ti(C5Me5)(Me3), Ba(thd)2*triglyme, Sr(thd)2*triglyme, Ti(thd)3, RuCp2 Ta(NMe2)5 and Ta(NMe2)3(NC9H11).
5. A method according to claim 1, wherein the concentration of the precursor in the precursor solution is from 0.01 M to 1 M.
6. A method according to claim 1, wherein the precursor solution further includes stabilizing additives with concentrations from 0.0001 M to 1 M, selected from the group consisting of oxygen containing organic compounds such as THF, 1,4-dioxane, and DMF.
7. A method according to claim 1, wherein the solvent has a boiling point selected to ensure no solvent loss during vaporization.
8. A method according to claim 1, wherein the solvent is selected form the group consisting of dioxane, toluene, n-butyl acetate, octane, ethylcyclohexane, 2-methoxyethyl acetate, cyclohexanone, propylcyclohexane, 2-methoxyethyl ether (diglyme), butylcyclohexane and 2,5-dimethyloxytetrahydrofuran.
9. A method according to claim 1, wherein the reaction solution is selected from the group consisting of water, oxygen, ozone, hydrogen, ammonia, silane, disilane, diborane, hydrogen sulfide, organic amines and hydrazines, or other gaseous molecule or plasma or radical sources.
10. A method according to claim 1, wherein delivery of the vaporized precursor solution comprises delivery at a flow rate from 10 nL/min to 10 ml/min.
11. A method according to claim 1, wherein the precursor solution is vaporized at a temperature from 100° C. and 350° C. and a pressure from −14 psig and +10 psig.
12. A method according to claim 1, further comprising purging the deposition chamber between each alternate delivery of vaporized precursor solution and vaporized reaction solution.
13. A method according to claim 12, wherein vaporized precursor solution is delivered for 0.1 to 10 seconds, a first purge is carried out for 1 to 10 seconds, vaporized reaction solution is delivered for 0.1 to 10 seconds, and a second purge is carried out for 1 to 10 seconds.
14. A method according to claim 1, wherein the precursor is aluminum i-propoxide, the solvent is ethylcyclohexane or octane and the thin film is Al2O3.
15. (canceled)
16. A method according to claim 1, wherein the precursor is Tetrakis(1-methoxy-2-methyl-2-propoxide) hafnium (IV), the solvent is ethylcyclohexance or octane and the thin film is HfO2.
17. A method according to claim 1, wherein the precursor is hafnium tert-butoxide or hafnium ethoxide, the solvent is ethylcyclohexane or octane and the thin film is HfO2.
18. A method according to claim 1, wherein the precursor is a mixture of Ba(O-iPr)2, Sr(O-iPr)2, and Ti(O-iPr)4, the solvent is ethylcyclohexane or octane and the thin film is BST.
19. A method according to claim 1, wherein the precursor is RuCp2, the solvent is dioxane, dioxane/octane or 2,5-dimethyloxytetrahydrofuran/octane and the thin film is Ru.
20. (canceled)
21. A method of atomic layer deposition comprising:
alternately delivering a vaporized precursor solution and a vaporized reaction solution to a deposition chamber;
forming a monolayer of components of the precursor solution and reaction solution on surface of a substrate in the deposition chamber; and
repeating until a thin film of predetermined thickness is formed;
wherein the vaporized precursor solution comprises one or more low volatility precursors dissolved in a solvent; and
wherein the precursor solution is delivered to a vaporizer at room temperature and vaporized without decomposition or condensation by operating the vaporizer at constant pressure.
22. A method according to claim 21, wherein constant pressure in the vaporizer is maintained by controlling pumping speed at an exit of the vaporizer and controlling liquid flow rate at the entrance to the vaporizer.
23. (canceled)
24. (canceled)
25. (canceled)
26. (canceled)
27. (canceled)
28. (canceled)
29. (canceled)
30. (canceled)
31. (canceled)
32. (canceled)
33. A thin film formed by an atomic layer deposition process, wherein a precursor solution used in the atomic layer deposition process comprises one or more low volatility precursors dissolved in a solvent, and wherein the precursor solution is vaporized without decomposition or condensation before use in the atomic layer deposition process.
34. A thin film according to claim 33, wherein the low volatility precursor is a solid.
35. A thin film according to claim 33, wherein the precursor solution is aluminum i-propoxide dissolved in ethylcyclohexane or octane and the thin film is Al2O3.
36. A thin film according to claim 33, wherein the precursor solution is [(t-Bu)Cp]2HfMe2, dissolved in ethylcyclohexane or octane and the thin film is HfO2.
37. A thin film according to claim 33, wherein the precursor solution is Tetrakis(1-methoxy-2-methyl-2-propoxide) hafnium (IV) dissolved in ethylcyclohexance or octane and the thin film is HfO2.
38. A thin film according to claim 33, wherein the precursor solution is hafnium tert-butoxide or hafnium ethoxide dissolved in ethylcyclohexane or octane and the thin film is HfO2.
39. A thin film according to claim 33, wherein the precursor solution is a mixture of Ba(O-iPr)2, Sr(O-iPr)2, and Ti(O-iPr)4 dissolved in ethylcyclohexane or octane and the thin film is BST.
40. A thin film according to claim 33, wherein the precursor solution is RuCp2 dissolved in dioxane, dioxane/octane or 2,5-dimethyloxytetrahydrofuran/octane and the thin film is Ru.
41. A thin film according to claim 33, wherein the thin film is free from impurity contamination.
42. A method according to claim 1 wherein the vaporized precursor solution and the vaporized reaction solution are both completely vaporized.
43. A method according to claim 1 wherein alternatively delivering comprises delivering using a vapor phase switching method.
44. A method according to claim 1 wherein alternatively delivering comprises delivering using a fast action pressure swing method.
45. A method of atomic layer deposition comprising:
alternately delivering a vaporized precursor solution and a vaporized reaction solution to a deposition chamber using a fast action pressure swing method;
forming a monolayer of components of the precursor solution and reaction solution on surface of a substrate in the deposition chamber; and
repeating until a thin film of a predetermined thickness is formed;
wherein the vaporized precursor solution comprises one or more low volatility precursors dissolved in a solvent.
US12/396,806 2005-04-29 2009-03-03 Method and apparatus for using solution precursors for atomic layer deposition Abandoned US20090220374A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US12/396,806 US20090220374A1 (en) 2005-04-29 2009-03-03 Method and apparatus for using solution precursors for atomic layer deposition
US13/298,574 US20120295038A1 (en) 2005-04-29 2011-11-17 Method and apparatus for using solution based precursors for atomic layer deposition
US13/298,563 US20120294753A1 (en) 2006-04-10 2011-11-17 Method and apparatus for using solution based precursors for atomic layer deposition

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US67649105P 2005-04-29 2005-04-29
US11/400,904 US7514119B2 (en) 2005-04-29 2006-04-10 Method and apparatus for using solution based precursors for atomic layer deposition
US12/396,806 US20090220374A1 (en) 2005-04-29 2009-03-03 Method and apparatus for using solution precursors for atomic layer deposition

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11/400,904 Continuation US7514119B2 (en) 2005-04-29 2006-04-10 Method and apparatus for using solution based precursors for atomic layer deposition

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US13/298,563 Continuation-In-Part US20120294753A1 (en) 2006-04-10 2011-11-17 Method and apparatus for using solution based precursors for atomic layer deposition
US13/298,574 Continuation-In-Part US20120295038A1 (en) 2005-04-29 2011-11-17 Method and apparatus for using solution based precursors for atomic layer deposition

Publications (1)

Publication Number Publication Date
US20090220374A1 true US20090220374A1 (en) 2009-09-03

Family

ID=36809616

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/400,904 Expired - Fee Related US7514119B2 (en) 2005-04-29 2006-04-10 Method and apparatus for using solution based precursors for atomic layer deposition
US12/396,806 Abandoned US20090220374A1 (en) 2005-04-29 2009-03-03 Method and apparatus for using solution precursors for atomic layer deposition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US11/400,904 Expired - Fee Related US7514119B2 (en) 2005-04-29 2006-04-10 Method and apparatus for using solution based precursors for atomic layer deposition

Country Status (7)

Country Link
US (2) US7514119B2 (en)
EP (3) EP2298957A3 (en)
JP (2) JP2006310865A (en)
KR (1) KR101332877B1 (en)
CN (2) CN101063196B (en)
SG (2) SG126910A1 (en)
TW (1) TWI393803B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9045826B2 (en) 2012-04-06 2015-06-02 Samsung Display Co., Ltd. Thin film deposition apparatus and thin film deposition method using the same

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI117979B (en) * 2000-04-14 2007-05-15 Asm Int Process for making oxide thin films
EP2029790A1 (en) 2006-06-02 2009-03-04 L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method of forming high-k dielectric films based on novel titanium, zirconium, and hafnium precursors and their use for semiconductor manufacturing
DE102006027932A1 (en) * 2006-06-14 2007-12-20 Aixtron Ag Method for the deposition of layers in a process chamber used in the production of electronic components comprises using a first starting material containing two beta-diketones and a diene coordinated with a ruthenium atom
US20100036144A1 (en) * 2006-07-20 2010-02-11 Ce Ma Methods for atomic layer deposition
JP5248508B2 (en) 2006-09-22 2013-07-31 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Method for depositing ruthenium-containing films
CN101617065B (en) 2007-02-21 2011-11-23 乔治洛德方法研究和开发液化空气有限公司 Methods for forming a ruthenium-based film on a substrate
JP5248025B2 (en) * 2007-03-01 2013-07-31 東京エレクトロン株式会社 Method for forming SrTiO3 film and computer-readable storage medium
US20080254218A1 (en) 2007-04-16 2008-10-16 Air Products And Chemicals, Inc. Metal Precursor Solutions For Chemical Vapor Deposition
US8142847B2 (en) * 2007-07-13 2012-03-27 Rohm And Haas Electronic Materials Llc Precursor compositions and methods
KR101227446B1 (en) * 2007-07-31 2013-01-29 삼성전자주식회사 Method of forming a ferro-electric layer and method of manufacturing a ferro-electric capacitor
JP4472008B2 (en) 2007-08-30 2010-06-02 株式会社日立国際電気 Semiconductor device manufacturing method and substrate processing apparatus
EP2191034B1 (en) * 2007-09-14 2013-03-13 Sigma-Aldrich Co. LLC Methods of preparing thin films by atomic layer deposition using monocyclopentadienyl triamino zirconium precursors
US20090117274A1 (en) * 2007-11-06 2009-05-07 Ce Ma Solution based lanthanum precursors for atomic layer deposition
KR100958332B1 (en) 2008-01-28 2010-05-18 (주)디엔에프 A new ruthenium compound and vapor deposition method using the same
JP5535945B2 (en) 2008-02-27 2014-07-02 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Method for forming a titanium-containing layer on a substrate using atomic layer deposition (ALD)
US8852460B2 (en) 2008-03-19 2014-10-07 Air Liquide Electronics U.S. Lp Alkali earth metal precursors for depositing calcium and strontium containing films
US8092721B2 (en) 2008-03-26 2012-01-10 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Deposition of ternary oxide films containing ruthenium and alkali earth metals
TWI447256B (en) * 2008-03-26 2014-08-01 Air Liquide Deposition of ternary oxide films containing ruthenium and alkali earth metals
WO2009119968A1 (en) * 2008-03-27 2009-10-01 Industry-Academic Cooperation Foundation, Yonsei University Oxide semiconductor thin film and fabrication method thereof
WO2009118901A1 (en) * 2008-03-28 2009-10-01 株式会社日立国際電気 Method for thin film formation
DE102008017077B4 (en) * 2008-04-01 2011-08-11 Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Process for the preparation of an n-semiconducting indium sulfide thin film
US7816200B2 (en) 2008-04-22 2010-10-19 Applied Materials, Inc. Hardware set for growth of high k and capping material films
US8741062B2 (en) * 2008-04-22 2014-06-03 Picosun Oy Apparatus and methods for deposition reactors
US8261908B2 (en) * 2008-12-05 2012-09-11 Linde Aktiengesellschaft Container for precursors used in deposition processes
US20100290968A1 (en) * 2009-05-13 2010-11-18 Ce Ma Solution based lanthanide and group iii precursors for atomic layer deposition
US20100290945A1 (en) * 2009-05-13 2010-11-18 Ce Ma Solution based zirconium precursors for atomic layer deposition
FR2950080B1 (en) * 2009-09-17 2012-03-02 Essilor Int METHOD AND DEVICE FOR GAS PHASE CHEMICAL DEPOSITION OF A POLYMER FILM ON A SUBSTRATE
US20110256314A1 (en) * 2009-10-23 2011-10-20 Air Products And Chemicals, Inc. Methods for deposition of group 4 metal containing films
US8859047B2 (en) 2010-02-23 2014-10-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Use of ruthenium tetroxide as a precursor and reactant for thin film depositions
US8357614B2 (en) 2010-04-19 2013-01-22 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Ruthenium-containing precursors for CVD and ALD
KR101234019B1 (en) * 2011-10-11 2013-02-18 주식회사 에스에프에이 Laminator for manufacturing oled
US9337018B2 (en) 2012-06-01 2016-05-10 Air Products And Chemicals, Inc. Methods for depositing films with organoaminodisilane precursors
US9978585B2 (en) * 2012-06-01 2018-05-22 Versum Materials Us, Llc Organoaminodisilane precursors and methods for depositing films comprising same
WO2015013630A1 (en) * 2013-07-26 2015-01-29 President And Fellows Of Harvard College Metal amides of cyclic amines
JP6258657B2 (en) * 2013-10-18 2018-01-10 東京エレクトロン株式会社 Film forming method and film forming apparatus
US10428421B2 (en) * 2015-08-03 2019-10-01 Asm Ip Holding B.V. Selective deposition on metal or metallic surfaces relative to dielectric surfaces
TW201823501A (en) 2016-11-16 2018-07-01 美商陶氏全球科技有限責任公司 Process for producing thin coatings on film
JP6954776B2 (en) 2017-06-29 2021-10-27 株式会社Adeka Raw material for thin film formation and manufacturing method of thin film
KR102103346B1 (en) * 2017-11-15 2020-04-22 에스케이트리켐 주식회사 Precursor Solution for Vapor Deposition and Fabrication Method of Thin Film Using the Same
US10975470B2 (en) * 2018-02-23 2021-04-13 Asm Ip Holding B.V. Apparatus for detecting or monitoring for a chemical precursor in a high temperature environment
EP3575004B1 (en) * 2018-05-29 2023-06-28 IMEC vzw Redox atomic layer deposition
SE543244C2 (en) 2019-03-06 2020-10-27 3Nine Ab Method and installation for reduction of sulphur dioxides in exhaust gases from a marine diesel engine
CN111501016A (en) * 2020-04-09 2020-08-07 中国科学院微电子研究所 High-uniformity atomic layer deposition method and application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6178925B1 (en) * 1999-09-29 2001-01-30 Advanced Technology Materials, Inc. Burst pulse cleaning method and apparatus for liquid delivery system
US20030008157A1 (en) * 2000-10-18 2003-01-09 Hiroshi Shiho Rutenium film rutenium oxide film, and method for formation thereof
US20030165615A1 (en) * 2002-01-29 2003-09-04 Titta Aaltonen Process for producing metal thin films by ALD
US6635114B2 (en) * 1999-12-17 2003-10-21 Applied Material, Inc. High temperature filter for CVD apparatus
US6664186B1 (en) * 2000-09-29 2003-12-16 International Business Machines Corporation Method of film deposition, and fabrication of structures
US20040043149A1 (en) * 2000-09-28 2004-03-04 Gordon Roy G. Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide
US20040079286A1 (en) * 2002-07-12 2004-04-29 Sven Lindfors Method and apparatus for the pulse-wise supply of a vaporized liquid reactant
US20040215029A1 (en) * 2003-04-24 2004-10-28 Tosoh Corporation Novel organometallic iridium compound, process of producing the same, and process of producing thin film
US6821845B1 (en) * 1998-10-14 2004-11-23 Hitachi, Ltd. Semiconductor device and method for manufacturing the same
US20040261850A1 (en) * 2003-06-26 2004-12-30 Maula Jarmo Ilmari Diaphragm valve for high-temperature precursor supply in atomic layer deposition
US7107998B2 (en) * 2003-10-16 2006-09-19 Novellus Systems, Inc. Method for preventing and cleaning ruthenium-containing deposits in a CVD apparatus

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9002164A (en) * 1990-10-05 1992-05-06 Philips Nv METHOD FOR PROVIDING A SUBSTRATE OF A SURFACE LAYER FROM A VAPOR AND AN APPARATUS FOR APPLYING SUCH A METHOD
US5376409B1 (en) 1992-12-21 1997-06-03 Univ New York State Res Found Process and apparatus for the use of solid precursor sources in liquid form for vapor deposition of materials
US5451260A (en) 1994-04-15 1995-09-19 Cornell Research Foundation, Inc. Method and apparatus for CVD using liquid delivery system with an ultrasonic nozzle
JPH11111644A (en) * 1997-09-30 1999-04-23 Japan Pionics Co Ltd Vaporization supplying equipment
JP2000026974A (en) * 1998-07-08 2000-01-25 Fujitsu Ltd Formation of thin film and thin film forming device
KR20010047128A (en) * 1999-11-18 2001-06-15 이경수 Method of vaporizing a liquid source and apparatus used therefor
DE10003758A1 (en) 2000-01-28 2001-08-02 Aixtron Gmbh Device and method for separating at least one precursor present in liquid or dissolved form
US6984591B1 (en) * 2000-04-20 2006-01-10 International Business Machines Corporation Precursor source mixtures
US7005392B2 (en) * 2001-03-30 2006-02-28 Advanced Technology Materials, Inc. Source reagent compositions for CVD formation of gate dielectric thin films using amide precursors and method of using same
US6420279B1 (en) * 2001-06-28 2002-07-16 Sharp Laboratories Of America, Inc. Methods of using atomic layer deposition to deposit a high dielectric constant material on a substrate
KR100468847B1 (en) * 2002-04-02 2005-01-29 삼성전자주식회사 Chemical vapor deposition method using alcohols for forming metal-oxide thin film
JP3670628B2 (en) * 2002-06-20 2005-07-13 株式会社東芝 Film forming method, film forming apparatus, and semiconductor device manufacturing method

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6821845B1 (en) * 1998-10-14 2004-11-23 Hitachi, Ltd. Semiconductor device and method for manufacturing the same
US6178925B1 (en) * 1999-09-29 2001-01-30 Advanced Technology Materials, Inc. Burst pulse cleaning method and apparatus for liquid delivery system
US6635114B2 (en) * 1999-12-17 2003-10-21 Applied Material, Inc. High temperature filter for CVD apparatus
US20040043149A1 (en) * 2000-09-28 2004-03-04 Gordon Roy G. Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide
US6664186B1 (en) * 2000-09-29 2003-12-16 International Business Machines Corporation Method of film deposition, and fabrication of structures
US20030008157A1 (en) * 2000-10-18 2003-01-09 Hiroshi Shiho Rutenium film rutenium oxide film, and method for formation thereof
US20030165615A1 (en) * 2002-01-29 2003-09-04 Titta Aaltonen Process for producing metal thin films by ALD
US20040079286A1 (en) * 2002-07-12 2004-04-29 Sven Lindfors Method and apparatus for the pulse-wise supply of a vaporized liquid reactant
US20040215029A1 (en) * 2003-04-24 2004-10-28 Tosoh Corporation Novel organometallic iridium compound, process of producing the same, and process of producing thin film
US20040261850A1 (en) * 2003-06-26 2004-12-30 Maula Jarmo Ilmari Diaphragm valve for high-temperature precursor supply in atomic layer deposition
US7107998B2 (en) * 2003-10-16 2006-09-19 Novellus Systems, Inc. Method for preventing and cleaning ruthenium-containing deposits in a CVD apparatus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9045826B2 (en) 2012-04-06 2015-06-02 Samsung Display Co., Ltd. Thin film deposition apparatus and thin film deposition method using the same

Also Published As

Publication number Publication date
EP2281922A3 (en) 2011-06-22
KR101332877B1 (en) 2013-11-25
US7514119B2 (en) 2009-04-07
JP2006310865A (en) 2006-11-09
JP2012214909A (en) 2012-11-08
US20060269667A1 (en) 2006-11-30
CN101063196A (en) 2007-10-31
EP2281922A2 (en) 2011-02-09
KR20060113556A (en) 2006-11-02
TWI393803B (en) 2013-04-21
CN101063196B (en) 2010-08-25
EP1717343A2 (en) 2006-11-02
TW200710267A (en) 2007-03-16
EP2298957A3 (en) 2011-06-22
SG126910A1 (en) 2006-11-29
SG160432A1 (en) 2010-04-29
EP2298957A2 (en) 2011-03-23
EP1717343A3 (en) 2007-12-12
CN101818335A (en) 2010-09-01

Similar Documents

Publication Publication Date Title
US7514119B2 (en) Method and apparatus for using solution based precursors for atomic layer deposition
US7544389B2 (en) Precursor for film formation and method for forming ruthenium-containing film
KR101274330B1 (en) Atomic layer deposition using alkaline earth metal beta-diketiminate precursors
US7335569B2 (en) In-situ formation of metal insulator metal capacitors
US8685165B2 (en) Metal oxide films
US20100034719A1 (en) Novel lanthanide beta-diketonate precursors for lanthanide thin film deposition
US20120295038A1 (en) Method and apparatus for using solution based precursors for atomic layer deposition
US20090117274A1 (en) Solution based lanthanum precursors for atomic layer deposition
KR100418569B1 (en) Method for forming high dielectric thin film using atomic layer deposition
US20100075067A1 (en) Preparation of Metal Oxide Thin Film Via Cyclic CVD or ALD
US8852460B2 (en) Alkali earth metal precursors for depositing calcium and strontium containing films
US20100290945A1 (en) Solution based zirconium precursors for atomic layer deposition
KR20120056827A (en) High dielectric constant films deposited at high temperature by atomic layer deposition
KR20120008015A (en) Method for making oriented tantalum pentoxide films
US20120294753A1 (en) Method and apparatus for using solution based precursors for atomic layer deposition
US20100003532A1 (en) Beta-diketiminate precursors for metal containing film deposition
US20100055321A1 (en) Precursors for atomic layer deposition
KR20050015441A (en) Method for Deposition of Hafnium Oxide Thin Films

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION