CN1734727A

CN1734727A - Use atom layer deposition process to make the method for metal silicate layer

Info

Publication number: CN1734727A
Application number: CNA200510091335XA
Authority: CN
Inventors: 金润奭; 金宗杓; 林夏珍; 朴哉彦; 丁炯硕; 李钟镐; 梁钟虎
Original assignee: Samsung Electronics Co Ltd
Current assignee: Samsung Electronics Co Ltd
Priority date: 2004-05-14
Filing date: 2005-05-16
Publication date: 2006-02-15
Anticipated expiration: 2025-05-16
Also published as: CN100479113C; KR100689824B1; KR20050109036A

Abstract

Provide and used atom layer deposition process on the semiconductor-based end, to make the method for metal silicate layer.In order to form the metal silicate layer with desired thickness, these methods comprise that carrying out metal silicate layer forms the cycle at least once.The metal silicate layer formation cycle comprises that repeating metal oxide layer forms cycle K time operation and repeat Si oxide formation cycle Q time operation.K and Q are respectively 1 to 10 integers, and this metal oxide layer formation cycle comprises step: accommodating metal source gas in the reactor that contains substrate, discharge the metal source gas that remains in the reactor, then to this reactor supply oxide gas.This silicon oxide layer formation cycle comprises: supply silicon source gas in the reactor that contains substrate, discharge the silicon source gas that remains in the reactor, then to this reactor supply oxide gas.

Description

Use atom layer deposition process to make the method for metal silicate layer

Technical field

The present invention relates to a kind of method of making the semiconductor device thin layer, particularly relate to the method for a kind of use ald (ADL) prepared metal silicate layer.

Background technology

Along with the demand growing, must make more and more littler as the transistor of forming semiconductor element and capacitor fabrication, to satisfy requirement to smaller szie to the high-integrated semiconductor device.Transistor and capacitor element generally include dielectric.Yet a lot of difficulties during the effort aspect reducing this type of dielectric overall size and thickness has caused making.

For example, if form too thinly, may cause the deterioration of the insulation property of gate dielectric as the thickness of the gate dielectric of a transistorized element.Usually with the material of silicon dioxide as the formation gate dielectric.It is reported that if wherein be reduced to about 15_ or littler at the thickness of silica, directly the leakage electric current that causes of tunnel effect obviously takes place to increase fast in by grid.As addressing the above problem one of method, the use of high-k dielectric is studied, even this high-k dielectric is used for the time marquis of thin dielectric layer, this high-k dielectric also has higher dielectric constant and lower leakage electric current than silicon dioxide layer.

In recent years, metal silicate layer is as proposing hafnium silicate (HfSiO _x) layer propose as high-k dielectric.When this type of metal silicate layer was applied to semiconductor transistor, this type of metal silicate layer was compared with other high-k dielectric, had good carrier mobility usually.

Make the method for the routine of such metal silicate layer and use physical vapor deposition (PVD) and chemical vapor deposition (CVD).As everyone knows, owing to cover and very poor interfacial characteristics with the very poor step of silicon base, this PVD technology has critical limitations.Because need to use high temperature to form film, and the thickness of film accurately need be controlled at the restriction on several _ deviation, CVD technology also has serious limitation.In addition, because the ratio of component is difficult to control in PVD or CVD film, have been found that the conventional method of this metal silicate layer of preparation is not suitable for preparing highly integrated semiconductor device.

Therefore, ald (ALD) technology as preparation have precise thickness metal silicate layer alternative method and to its research, it overcomes limitation in CVD and the PVD technology by the atomic layer unit.In order to form film, this ALD technology is by the controlled method that source gas is provided with the Discrete Pulse stamp in order successively of time-sharing format, rather than the method for source gas is provided simultaneously.The supply of all gases can be carried out like this, promptly by time variance, drive/close valve that all gases is provided so that the gas of work does not mix mutually, and every source gas can be fed in the reactor at interval according to preset time respectively.When each source gas with such time variance during with predetermined flow velocity supply, also supplied a kind of purge gas in the time interval of gas to remove the responseless source gas that remains in the reactor providing.This ALD technology has such advantage, and it provides good step to cover, and deposits uniform film on large-scale substrate, and makes the thickness of film accurately to control by the number of times in control repeated deposition cycle.

The method of using ALD technology to make the routine of metal silicate has been disclosed in denomination of invention and is " METHOD FOR DEPOSITING A COATING HAVING A RELATIVELY HIGHDIELECTRIC CONSTANT ONTO A SUBSTRATE " (the basad method that deposits the coating with relative high-k that goes up), publication number is 2003-0031793, the invention people is in the U.S. Patent application of Cheng etc., at this, also the disclosure document is incorporated herein by reference.

According to Cheng etc., will be as the aluminium oxide (Al of metal oxide layer ₂O ₃) layer, tantalum oxide (Ta ₂O ₅) layer and hafnium oxide (HfO ₂) layer, and as the zirconium silicate (SiZrO of metal silicate layer ₄) layer and hafnium silicate (HfSiO _x) layer or the like be formed at the semiconductor-based end.Particularly, at Cheng etc., this semiconductor-based end, be loaded in the reactor.First original gas is fed to the whole surface of suitable substrates, then it is removed from reative cell.Then, by using oxide gas, as oxygen, steam, nitrous oxide (N ₂O) etc., make this be absorbed in the whole lip-deep first original oxidation of substrate.Repeat these operations until in substrate, forming the first film with desired thickness.Then, second original gas is fed to the whole surface that is deposited on suprabasil the first film and subsequently it being cleaned.Then, by using oxide gas, as oxygen, steam, nitrous oxide (N ₂O) etc., make this be absorbed in the whole lip-deep second original oxidation of suprabasil the first film.Repeat these operations and have the metal silicate layer of desired thickness until on the first film layer, forming.

Denomination of invention is " METHOD OF FABRICATING A SEMICONDUCTORDEVICE AND AN APPARATUS OF PROCESSING A SUBSTRATE " (preparing the method for semiconductor device and the equipment of processing substrate), disclose another in the Japan Patent of publication number 2003-347298 and made the method for metal silicate layer, at this, the disclosure thing also is introduced into as a reference.

According to the Japan Patent of patent publication No. 2003-347298, can make and comprise hafnium silicate (HfSiO _x) layer high-k dielectric.Particularly, ground floor source material gas is fed to suitable semiconductor surface then with its flush away from reative cell.Then, carrying out remote plasma oxidation (RPO) method comes to being absorbed in suprabasil ground floor source material supply oxygen radical.In order to form the ground floor of desired thickness, repeat to implement these operating procedures with the repetition period number of determining.Then the second material source gas is fed on the surface of structure of formation, then the surface of this layer is handled, that is, carry out RPO method to this surface supply oxygen radical.Repeat these operating procedures with the repetition period number of determining, to form the film of desired thickness.

When metal silicate layer is when disclosed method forms in U.S. Patent Application Publication No. 2003-0031793 or Japanese patent application publication No. 2003-347298, after the repetition period operation metal oxide layer formation step repetition with quantification, a kind of silicon source gas is fed on this structure.Usually, such silicon source gas has with respect to the chemically stable structure of metal oxide layer.Therefore, use such silicon source gas that there are a lot of limitations in the method that this metal oxide layer is transformed into the required metal silicate layer that obtains.For example, have been found that repeating to supply silicon source gas in view of the above after metal oxide layer forms step 10 time or more times that it is unusual difficulty that this metal oxide layer is transformed into metal silicate layer.The technical process that replaces this type of to cause required metal silicate layer to form, silicon oxide layer may be stacked on respectively on the metal oxide layer, and perhaps the reaction of silicon oxide layer and/or formation may not take place or be along this surface portion generation and inhomogeneous on metal oxide layer.

Summary of the invention

Therefore, the invention provides a kind of method of making metal silicate layer on the suitable semiconductor-based end, wherein this method can accurately be controlled the thickness of film and can control the ratio of components of metal and silicon in the metal silicate layer of this generation.

The present invention another more specifically purpose provide a kind of hafnium silicate layer of on semiconductor substrate, making, can also accurately control the thickness of film and the method for the ratio of components of hafnium and silicon in the hafnium silicate layer that generates of control also simultaneously.

According to a typical embodiment, the invention provides a kind of method of using atom layer deposition process to make metal silicate layer.For the surface in substrate forms the chemical absorbing layer that comprises metal, this method generally includes the step of order: a substrate is installed in reactor or the reative cell, then the suitable metal source gas of supply in reactor with substrate or reative cell.Usually carry out cleaning step subsequently, oxide gas is fed to makes itself and the chemical absorbing layer reaction that comprises metal in the reactor, thereby in this substrate, form a metal oxide layer.To form the number that the sequential steps of metal oxide layer (metal/oxide step) repeats to determine, for example K time to reactor accommodating metal source gas, cleaning and supply oxide gas.Then in order to form the chemical absorbing layer that comprises silicon on the suprabasil metal oxide layer aforementioned being formed at, the suitable silicon source gas of supply in this reactor.Usually carry out cleaning step subsequently, oxide gas is fed to makes the chemical absorbing layer reaction that comprises silicon thereon of itself and metal oxide layer and deposition in the reactor, thereby form a metal silicate layer.Supply the number that operation that silicon source gas, cleaning and supply oxide gas form metal silicate layer repeats to determine, for example Q time with this to reactor.Be at least 2 one of in K and the Q value.To begin with the step of supply metal source gas to carry out at least once, and can carry out 2 times or more times, have the metal silicate layer of desired thickness thereby form to the complete and continuous operation that forms metal silicate layer.

According to typical embodiments of the present invention, this method can further comprise such correlation step valuably, as supplying various reacting gas after-purifications (or cleaning) this reactor.Particularly, remaining in unreacted metal source gas residual in the reactor after formation comprises the step of chemical absorbing layer of metal can be discharged to purify the inside of this reactor.After forming the step of metal oxide layer, remain in the unreacted oxide gas in the reactor and the byproduct of reaction of any gaseous state and can be discharged to purify the inside of this reactor.After formation comprised the step of chemical absorbing layer of silicon, the unreacted silicon source gas that remains in the reactor can similarly be discharged to purify the inside of this reactor.After forming metal silicate layer, remain in the unreacted oxide gas in the reactor and the byproduct of reaction of any gaseous state and can be discharged to purify the inside of this reactor.In an invention embodiment,, can in reactor, supply a kind of purge gas in order to discharge unreacted oxide gas and accessory substance.This purge gas will comprise basic inert gasses (with respect to reaction environment) usually, for example, and argon gas (Ar), helium (He), or nitrogen (N ₂).

As top defined cycle repeat number K and Q preferably 1 to about 10 scope.For example, for some common application, number K is favourable in the scope of 2-5, and number Q can be 1.Yet, have been found that the metal oxide layer that forms has chemically stable structure if number K is 10 or bigger in the operation that forms metal oxide layer.Because such metal oxide layer (wherein K 〉=10) has chemically stable structure, it makes and forms successful and general even metal silicate layer difficulty more.In addition, have been found that if number Q is 10 or bigger, even further supply silicon source gas to metal silicate layer, the chemical absorbing layer that contains silicon also forms usually.That is to say that if number Q is 10 or bigger, metal silicate layer can further not form again.Can use chemical general formula M according to metal silicate layer of the present invention _xSi _1-xO ₂Expression, wherein, M is the element that is selected from the group of being made up of Hf, Zr and Ti, and " x " represents the ratio of components of metal and silicon in this metal silicate layer.Form in the process of operation at this layer, by determining and control number K and Q that " x " controlled, for example in the scope of about 0.10-0.95.More preferably, " x " can be controlled in the scope of about 0.65-0.85.That is to say,, can on the semiconductor-based end, form and have the metal silicate layer of required ratio of components by controlling diaphragm number of deposition cycles (being respectively K and Q) suitably.

According to a typical embodiments more specifically, the invention provides a kind of by using atom layer deposition process on the suitable semiconductor-based end, to make the method for hafnium silicate layer.This method generally includes the step of order: a substrate is installed in reactor or the reative cell, then supply four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH in reactor with substrate or reative cell ₃) C ₂H ₅] ₄) gas to be to form the chemical absorbing layer comprise hafnium (Hf) on substrate surface.Usually carry out cleaning step subsequently, oxide gas is fed to makes itself and the chemical absorbing layer reaction that comprises hafnium (Hf) in the reactor, thereby in this substrate, form a hafnium (Hf) oxide skin(coating).This is formed the number that the operation of the order of hafnium oxide layer repeats to determine, for example K time to reactor supply TEMAH gas, cleaning and supply oxide gas.Then, in this reactor, supply disilicone hexachloride (HCD) (Si ₂Cl ₆) gas, to form the chemical absorbing layer that comprises silicon on the suprabasil hafnium oxide layer aforementioned being formed at.Usually carry out another cleaning step subsequently, oxide gas is fed to makes the chemical absorbing layer reaction that comprises silicon thereon of itself and hafnium (Hf) oxide skin(coating) and deposition in the reactor, thereby form a hafnium silicate (Hf _xSi _1-xO ₂) layer.This is formed the number that the operation of hafnium silicate layer repeats to determine, for example Q time to reactor supply HCD gas, cleaning and supply oxide gas.Be at least 2 one of in K value and the Q value.To begin to carry out at least once with the step of supply TEMAH gas, and can carry out 2 times or more times, thereby form hafnium silicate layer with desired thickness to the complete operation in tandem that forms the hafnium silicate layer.

According to typical embodiment of the present invention, this method can further comprise such correlation step valuably, as supplying various reacting gas after-purifications (or cleaning) this reactor.Particularly, comprise the step of chemical absorbing layer of hafnium in formation after, can discharge the unreacted TEMAH gas that remains in the reactor and can be discharged to purify the inside of this reactor.After the step that forms hafnium (Hf) oxide skin(coating), remain in the unreacted oxide gas in the reactor and the byproduct of reaction of any gaseous state and can be discharged to purify the inside of this reactor.After formation comprised the step of chemical absorbing layer of silicon, the unreacted HCD gas that remains in the reactor can similarly be discharged to purify the inside of this reactor.After forming the hafnium silicate layer, remain in the unreacted oxide gas in the reactor and the byproduct of reaction of any gaseous state and can be discharged to purify the inside of this reactor.The example that is used for the suitable purge gas of this type of reactor purifying step is aforesaid.

As above-mentioned defined cycle repeat number K and Q preferably 1 to about 10 scope.For example, number K can be in the scope of 2-5, and number Q can be 1.Yet, have been found that the hafnium oxide layer that forms has chemically stable structure if number K is 10 or bigger in the operation that forms hafnium oxide layer.Because such hafnium oxide layer (wherein K 〉=10) has chemically stable structure, it makes and forms successful and general uniform hafnium silicate layer difficulty more.In addition, have been found that if number Q is 10 or bigger, even further supply disilicone hexachloride (HCD) (Si to the hafnium silicate layer ₂Cl ₆) gas, can not form the chemical absorbing layer that contains silicon usually yet.That is to say that if number Q is 10 or bigger, the hafnium silicate layer can further not form again.Hafnium silicate layer according to the present invention can be used chemical general formula Hf _xSi _1-xO ₂Expression, wherein, " x " represents the ratio of components of hafnium in this metal silicate layer (Hf) with respect to hafnium+silicon.Form in the process of operation at this layer,, can control " x ", for example in the scope of about 0.10-0.95 by determining and control number K and Q.More preferably, can control " x " in the scope of about 0.65-0.85.That is to say,, can in substrate, form hafnium silicate (Hf with required ratio of components by controlling diaphragm number of deposition cycles (being respectively K and Q) suitably _xSi _1-xO ₂) layer.

According to other typical embodiment, the present invention also provides the method for other somewhat similar manufacturing hafnium silicate layer.This type of other method generally includes the step of order: a substrate is installed in reactor or the reative cell, then supply four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH in the reactor with substrate ₃) C ₂H ₅] ₄) gas, on substrate surface, to form the chemical absorbing layer that comprises hafnium (Hf).Usually carry out cleaning step subsequently, oxide gas is fed to makes itself and the chemical absorbing layer reaction that comprises hafnium (Hf) in the reactor, thereby in this substrate, form a hafnium (Hf) oxide skin(coating).To supply the number that operation that TEMAH gas, cleaning and supply oxide gas form the order of hafnium oxide layer repeats to determine, for example K time to reactor.Then, in this reactor, supply three (dimethylamino) silane (TDMAS) ([(CH ₃) ₂N] ₃SiH)) gas is to form the chemical absorbing layer that comprises silicon aforementioned being formed on the suprabasil hafnium oxide layer.Usually carry out another cleaning step subsequently, oxide gas is fed to makes the chemical absorbing layer reaction that comprises silicon thereon of itself and hafnium (Hf) oxide skin(coating) and deposition in the reactor, thereby form a hafnium silicate (Hf _xSi _1-xO ₂) layer.To supply the number that operation that TDMAS gas, cleaning and supply oxide gas form the hafnium silicate layer repeats to determine, for example Q time to reactor.Be at least 2 one of in K value and the Q value.To begin to carry out at least once with the step of supply TEMAH gas, and can carry out 2 times or more times, thereby form hafnium silicate layer with desired thickness to the complete operation in tandem that forms the hafnium silicate layer.

According to typical embodiments of the present invention, this method can further comprise such correlation step valuably, as supplying various reacting gas after-purifications (or cleaning) this reactor.Particularly, comprise the step of chemical absorbing layer of hafnium (Hf) in formation after, the unreacted TEMAH gas that remains in the reactor can be discharged to purify the inside of this reactor.After the step that forms hafnium (Hf) oxide skin(coating), remain in the unreacted oxide gas in the reactor and the byproduct of reaction of any gaseous state and can be discharged to purify the inside of this reactor.After formation comprised the step of chemical absorbing layer of silicon, the unreacted TDMAS gas that remains in the reactor can similarly be discharged to purify the inside of this reactor.After forming the hafnium silicate layer, remain in the unreacted oxide gas in the reactor and the byproduct of reaction of any gaseous state and can be discharged to purify the inside of this reactor.The example that is used for the suitable purge gas of this type of reactor purifying step is aforesaid.

As above-mentioned defined cycle repeat number K and Q preferably 1 to about 10 scope.For example, number K can be in the scope of 1-3, and number Q can be 1.Yet, have been found that the hafnium oxide layer that forms has chemically stable structure if number K is 10 or bigger in the operation that forms hafnium oxide layer.Because such hafnium oxide layer (wherein K 〉=10) has chemically stable structure, it makes and forms successful and general uniform hafnium silicate layer difficulty more.In addition, have been found that if number Q is 10 or bigger, even further supply three (dimethylamino) silane (TDMAS) ([(CH to the hafnium silicate layer ₃) ₂N] ₃SiH) gas can not form the chemical absorbing layer that contains silicon usually yet.That is to say that if number Q is 10 or bigger, the hafnium silicate layer can further not form again.Hafnium silicate layer according to the present invention can be used chemical general formula Hf _xSi _1-xO ₂Expression, wherein, " x " represents the ratio of components of hafnium in this metal silicate layer (Hf) with respect to hafnium+silicon.Form in the process of operation at this layer,, can control " x ", for example in the scope of about 0.10-0.95 by determining and control number K and Q.More preferably, can control " x " in the scope of about 0.65-0.85.That is to say,, can in substrate, form hafnium silicate (Hf with required ratio of components by controlling diaphragm number of deposition cycles (being respectively K and Q) suitably _xSi _1-xO ₂) layer.

Description of drawings

For the person of ordinary skill of the art, by describing the preferred embodiments of the invention in further detail with reference to appended accompanying drawing, the present invention above-mentioned and further feature and advantage will become more apparent, wherein:

Fig. 1 is the process chart that the method for ALD technology manufacturing metal silicate layer used according to the invention is described substantially;

Fig. 2 is the schematic diagram of the single complete layer deposition cycle (it can comprise several Q of several K of metal/oxide step and a large amount of silicon/oxide step) of a kind of ALD technology used according to the invention of explanation method of making metal silicate layer;

Fig. 3 is that explanation is formed at different hafnium silicate layer thickness at the semiconductor-based end to the curve chart along the curve plotting that locates at interval of the semiconductor-based end according to embodiment of the present invention;

Fig. 4 to Fig. 6 is according to the present invention, and the curve chart of several metal silicate layer thicknesses contrasts that the injection length according to metal source gas changes is described;

Fig. 7 be explanation in the process of metal silicate layer formed according to the present invention, deposit thickness is the curve chart that how changes according to the injection rate of metal source gas and silicon source gas;

Fig. 8 to Figure 11 be the explanation according to the present invention the deposition representative the different hafnium silicate (Hf of different ratio of componentss (" x ") _xSi _1-xO ₂) curve chart of x-ray photoelectron spectroscopy (XPS) analysis result of layer;

Figure 12 be explanation according to the change of formation periodicity of the present invention, the thickness of hafnium silicate layer and the curve chart that changes;

Figure 13 be the explanation according to embodiments of the invention for different hafnium silicate layers, the curve chart of the different leakage current deteriorations of leakage current;

Figure 14 illustrates for different according to an embodiment of the invention hafnium silicate layers the curve chart of the mutual conductance (Gm) and the different degradation characteristic of threshold voltage (Vth);

Figure 15 illustrates that for different according to an embodiment of the invention hafnium silicate layers, hot carrier is injected the curve chart of the various durations characteristic of (HCI);

Figure 16 illustrates for different according to an embodiment of the invention hafnium silicate layers the curve chart of the various durations characteristic of positive bias temperature instability (PBTI).

Embodiment

Now, hereinafter with reference to the accompanying drawing that shows the preferred embodiment of the invention, the present invention is described more fully.Yet, should be appreciated that the present invention can implement with a lot of different modes, therefore should not be regarded as only being confined to the embodiment that set forth in this place.On the contrary, it is in order to make the disclosure thorough and complete that these embodiments are provided, and gives full expression to scope of the present invention to those skilled in the art.In whole specification, identical numeral is used for representing components identical in the accompanying drawing.

Fig. 1 illustrates the process chart of making the method for metal silicate layer according to use according to the present invention ALD technology substantially, and Fig. 2 is the schematic diagram of the single complete layer deposition cycle of a kind of ALD technology used according to the invention of explanation method of making metal silicate layer.

See figures.1.and.2, comprise the suitable semiconductor-based end is encased in according to the conventional method of the manufacturing metal silicate layer of embodiment of the present invention comprising ald (ALD) system (reactor of the step 5) part of Fig. 1 or the initial or preliminary step in the reative cell.

Reactor can be sheet type or batch type.Substrate can be the semiconductor-based end, and for example silicon base, and this substrate can have the separator that has formed thereon.In addition, this substrate can have a kind of three-dimensional structure, the hearth electrode of the columniform capacitor that forms thereon for example, and it can comprise a plurality of different surface that is positioned on the Different Plane thus.These methods of the present invention can be used on any one or all surface of this type of substrate surface, forming metal silicate layer.

The inside of reactor is heated to the temperature that is fit to carry out preparation method of the present invention.For example, be used for the preference temperature of these methods in about 250 ℃-600 ℃ scope.

Repeat metal oxide layer and form cycle 10 (comprising

single step

11,13,15 and 17 separately) K time in substrate, formation has the metal oxide layer of desired thickness thus.This metal oxide layer formation cycle 10 can comprise single step: the accommodating metal source gas (step 11) of Fig. 1, discharge remains in the inside (step 13) of Fig. 1 of unreacted metal source gas to purify this reactor in the reactor, a kind of oxide gas of supply (step 15) of Fig. 1, and the inside of purification reactor (step 17 of Fig. 1) in this reactor.

Particularly, this metal source gas is fed to the (step 11) of Fig. 1 in the reactor that has wherein loaded substrate.In one embodiment, this metal source gas is a kind of chemical general formula MX that has ₄Material, wherein M is the element that is selected from the group of being made up of Hf, Zr and Ti, and X is the element that is selected from the group of being made up of F, Cl, Br and I.In another embodiment, this metal source gas is a kind of chemical general formula M (NRR ') that has ₄Material, wherein M is selected from by Hf, the element in the group that Zr and Ti form, N is a nitrogen, R be selected from by H, Me, Et and ⁱChemical group in the group that Pr forms, R ' be selected from by H, Me, Et and ¹Chemical group in the group that Pr forms.In addition, this metal source gas specifically also can be four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH ₃) C ₂H ₅] ₄).For example, under the situation of supply TEMAH, the burst length that is used for accommodating metal source gas can be about 0.2-2 second.Therefore, the exposed surface along this substrate has formed the chemical absorbing layer that comprises this metal.After the chemosphere that comprises this metal forms, with the inside (step 13) of Fig. 1 of metal source gas discharge that remains in the reactor to purify this reactor.In order to discharge this metal source gas, perhaps, can supply a kind of purge gas to the inside of this reactor in order to help such step.This purge gas generally includes basic inert gasses, for example argon gas (Ar), helium (He) or nitrogen (N ₂).Then, this oxide gas is fed to the (step 15) of Fig. 1 in this reactor.In addition, the oxide gas that is fed in the reactor can be to be selected from by oxygen (O ₂), ozone (O ₃), water (H ₂O) and hydrogen peroxide (H ₂O ₂) at least a in the group formed.Therefore, this chemical absorbing layer and this oxide gas react each other, to such an extent as to form this metal oxide layer in substrate.Then, with the inside (step 17 of Fig. 1) of gaseous by-product discharge that remains in the oxide gas in the reactor and produce to purify this reactor by the reaction of chemical absorbing layer and oxide gas.In order to discharge this oxide gas and byproduct of reaction, perhaps help such step, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, for example argon gas (Ar), helium (He) or nitrogen (N ₂).Manually or automatically check then, to determine whether to have formed metal oxide layer with desired thickness.This metal oxide layer formation cycle 10 is repeated K time until form the metal oxide layer (step 19 of Fig. 1) with desired thickness in substrate.Counting K here, is at 1 integer to about 10 scopes.That is to say that metal/oxide layers forms the repeat number K in cycle 10 preferably in 1 time to 10 times scope.

Next, in metal oxide layer substrate formed thereon, repeat silicon oxide layer formation cycle 20 (

single step

21,23,25 and 27 that comprises separation) Q time.This silicon oxide layer formation cycle 20 can comprise independent step: supply silicon source gas (step 21 of Fig. 1), discharge remains in the inside (step 23 of Fig. 1) of unreacted silicon source gas to purify this reactor in the reactor, to this reactor supply oxide gas (step 25 of Fig. 1), and the inside (step 27 of Fig. 1) that purifies this reactor.

Particularly, this silicon source gas is fed to (step 21 of Fig. 1) in the reactor that has wherein loaded substrate.In one embodiment, this silicon source gas is a kind of chemical general formula Si that has _nX ' _2n+2Material, wherein n is the number in about 1-4 scope, and X ' is chemical group or the element that is selected from the group of being made up of NCO, F, Cl, Br and I.In another embodiment, this silicon source gas is a kind of chemical general formula Si that has _nX ' _2n+2O _N-1Material, wherein n is the number in about 2-5 scope, X ' is chemical group or the element that is selected from the group of being made up of NCO, F, Cl, Br and I.In another embodiment, this silicon source gas is a kind of chemical general formula Si that has _nX " _n(NRR ') _4-nMaterial, wherein n can be the number in about 0-3 scope, X " can be chemical group or the element that is selected from the group of forming by H, F, Cl, Br and I; R can be selected from by H, Me, Et and ⁱChemical group or element in the group that Pr forms; And R ' be selected from by H, Me, Et and ⁱChemical group or element in the group that Pr forms.In another embodiment of the invention, this silicon source gas is a kind of chemical general formula NH that has _n(SiR " ₃) _3-nMaterial, wherein n can be the number in about 0-2 scope, N is a nitrogen, and R " be selected from by H, F, Cl, Br, I, Me, Et and ⁱChemical group or element in the group that Pr forms.In another embodiment of the invention, this silicon source gas is a kind of chemical general formula SiSX that has ₂Material, wherein S is a sulphur, and X can be chemical group or the element that is selected from the group of being made up of F, Cl, Br and I.In another specific embodiments of the present invention, this silicon source gas can be disilicone hexachloride (HCD) (Si ₂Cl ₆).In addition, this silicon source gas can be three (dimethylamino) silane (TDMAS) ([(CH ₃) ₂N] ₃SiH).As result's (step 21) of supply silicon source gas step, the chemical absorbing layer that comprises silicon is formed on to have on the substrate surface that is formed with metal oxide layer thereon.After this chemical absorbing layer that contains silicon forms, with the inside (step 23 of Fig. 1) of silicon source gas discharge that remains in the reactor to purify this reactor.In order to discharge this silicon source gas, perhaps help such step, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, for example argon gas (Ar), helium (He) or nitrogen (N ₂).Then, this oxide gas is fed to (step 25 of Fig. 1) in this reactor.This oxide gas can be to be selected from by oxygen (O ₂), ozone (O ₃), water (H ₂O) and hydrogen peroxide (H ₂O ₂) at least a in the group formed.For example, be under the situation of HCD in this silicon source, preferred oxide gas can be H ₂O.If this silicon source is TDMAS, preferred oxide gas can be ozone (O ₃).Therefore, this chemical absorbing layer and this oxide gas react each other, make to form this silicon oxide layer in substrate.While or simultaneously basic at least,, this metal oxide layer and this Si oxide gas forms this metal silicate layer to such an extent as to reacting each other.Then, with the inside (step 27 of Fig. 1) of gaseous by-product discharge that remains in the oxide gas in the reactor and produce to purify this reactor by the reaction of chemical absorbing layer and oxide gas.In order to discharge this oxide gas and byproduct of reaction, perhaps help such step, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, argon gas (Ar) for example, helium (He), or nitrogen (N ₂).Manually or automatically check then, to determine whether to have formed metal silicate layer with required ratio of components.This silicon oxide layer is formed cycle 20 to be repeated Q time and has the metal silicate layer (step 29 of Fig. 1) of required ratio of components until formation in substrate.Counting Q here, is at 1 integer to about 10 scopes.That is to say that silicon/oxide skin(coating) forms the repeat number Q in cycle 20 preferably in 1 time to 10 times scope.

In manufacturing metal silicate method according to the preferred embodiment of the invention, must determine number K and Q respectively, it is no more than 10 times.For example, number K can be in the scope of 2-5, and number Q can be 1.More preferably, number K can be 3, and number Q can be 1.If number K is 10 or bigger, form the highly stable chemically stable structure of metal oxide layer acquisition that the cycle 10 forms by metal oxide layer.Yet, form metal oxide layer and make that the formation metal silicate layer is very difficult in the silicon oxide layer process in formation cycle 20 with this type of chemically stable structure.That is to say that because this has the metal oxide layer of chemically stable structure, this silicon oxide layer can change into and being sticked to respectively on the metal oxide layer with aforesaid chemically stable structure, and/or silicon oxide layer formation reaction may not take place.In addition, if number Q is 10 or bigger, even further supply silicon source gas to metal silicate layer, the chemical absorbing layer that contains silicon can not form usually yet.That is to say that be carried out above 10 times even this silica layer forms the cycle 20, extra metal silicate layer does not further form usually yet.Formed metal silicate layer can be used chemical general formula M according to the present invention _xSi _1-xO ₂Expression, wherein, M can be the element that is selected from the group of being made up of Hf, Zr and Ti, and " x " represents in this metal silicate layer metal with respect to the ratio of components of metal+silicon.By controlling several K and the Q of repetition period rightly respectively, can control " x " in the scope of about 0.10-0.95.More preferably, can control " x " in the scope of about 0.65-0.85.That is to say to have the metal silicate layer of required ratio of components " x " by controlling the periodicity K and the silicon/oxide periodicity Q of metal/oxide, can on the semiconductor-based end, forming.

Therefore, this metal silicate layer formation cycle comprises that carrying out K this metal oxide layer forms the operation in cycle 10 and comprise the operation of carrying out Q this silicon oxide layer formation cycle 20.Then, check the thickness (step 39 of Fig. 1) of this metal silicate layer.This metal silicate layer formation cycle carries out at least once, or repeats to have the metal silicate layer of desired thickness until forming in this substrate.That is to say, repeat K time and carry out this metal oxide layer formation cycle 10, next repeat Q time and carry out this silicon oxide layer formation cycle 20, such operating sequence is carried out one or many, has the metal silicate layer of desired thickness up to forming on this basalis.

More specifically, according to embodiment of the present invention, can form a kind of hafnium silicate (Hf _xSi _1-xO ₂) layer.Hereinafter, with reference to Fig. 1 and Fig. 2, illustrate a kind of this hafnium silicate (Hf for preparing according to embodiments of the present invention _xSi _1-xO ₂) layer method.

The method for preparing this hafnium silicate layer comprises reactor part (the initial or preliminary step of the step 5) of Fig. 1 that is encased in ALD equipment the suitable semiconductor-based end.

This inside with reactor is heated to the temperature that is suitable for carrying out manufacture method of the present invention.For example, can be in about 250 ℃-600 ℃ scope to the suitable temperature of these methods.

Hafnium oxide layer being formed the cycle 10 in substrate repeats K time, thereby forms hafnium (Hf) oxide skin(coating) with desired thickness.This hafnium oxide layer formation cycle 10 can comprise independent step: supply hafnium (Hf) source gas (step 11) of Fig. 1, discharge remains in the inside (step 13) of Fig. 1 of unreacted hafnium (Hf) source gas to purify this reactor in the reactor, a kind of oxide gas of supply (step 15) of Fig. 1, and the inside of purification reactor (step 17 of Fig. 1) in this reactor.

Particularly, this hafnium (Hf) source gas is fed to the (step 11) of Fig. 1 in the reactor that has wherein loaded substrate.In one embodiment, this hafnium (Hf) source gas is a kind of chemical general formula HfX that has ₄Material, and X is selected from by F, Cl, the element in the group that Br and I form.In another embodiment, this hafnium (Hf) source gas is a kind of chemical general formula Hf (NRR ') that has ₄Material, wherein R is selected from by H, Me, Et and ⁱChemical group in the group that Pr forms, and R ' is selected from by H, Me, Et and ⁱChemical group in the group that Pr forms.In addition, this hafnium source gas specifically can also be four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH ₃) C ₂H ₅]) ₄).For example, if supply TEMAH, the burst length that is used for accommodating metal source gas can be about 0.2-2 second.Therefore, the exposed surface along this substrate has formed the chemical absorbing layer that comprises hafnium.After the chemosphere that comprises hafnium (Hf) forms, with the inside (step 13) of Fig. 1 of hafnium (Hf) source gas discharge that remains in the reactor to purify this reactor.In order to discharge this hafnium (Hf) source gas, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, argon gas (Ar) for example, helium (He), or nitrogen (N ₂).Then, this oxide gas is fed to the (step 15) of Fig. 1 in this reactor.This oxide gas can be to be selected from by oxygen (O ₂), ozone (O ₃), water (H ₂O) and hydrogen peroxide (H ₂O ₂) at least a in the group formed.If TEMAH is used as hafnium (Hf) source gas, this oxide gas is ozone (O preferably ₃).The easy oxidation of ozone may be adhered to the typical impurity on the hafnium.That is to say that this ozone treatment is removed the impurity on the hafnium effectively.Therefore, this chemical absorbing layer and this oxide gas react each other, make to form this hafnium (Hf) oxide skin(coating) in substrate.Then, with the inside (step 17 of Fig. 1) of gaseous by-product discharge that remains in the oxide gas in the reactor and produce to purify this reactor by chemical absorbing layer and oxide gas reaction.In order to discharge this oxide gas and byproduct of reaction, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, argon gas (Ar) for example, helium (He), or nitrogen (N ₂).Manually or automatically check then, to determine whether to have formed hafnium (Hf) oxide skin(coating) with desired thickness.This hafnium (Hf) oxide skin(coating) formation cycle 10 is repeated K time until form hafnium (Hf) oxide skin(coating) (step 19 of Fig. 1) with desired thickness in substrate.Counting K here, is at 1 integer to about 10 scopes.That is to say that hafnium/oxide skin(coating) forms the repeat number K in cycle 10 preferably in 1 time to 10 times scope.

Next, form thereon and have in the substrate of hafnium (Hf) oxide skin(coating), silicon oxide layer is formed the cycle 20 repeat Q time, thus formation hafnium silicate layer.This silicon oxide layer formation cycle 20 can comprise independent step: supply silicon source gas (step 21 of Fig. 1), discharge remains in the inside (step 23 of Fig. 1) of unreacted silicon source gas to purify this reactor in the reactor, to this reactor supply oxide gas (step 25 of Fig. 1), and the inside (step 27 of Fig. 1) that purifies this reactor.

Particularly, according to embodiment of the present invention, this hafnium silicate layer can the general mode identical with the method illustrated among reference Fig. 1 and 2 form.For example, this silicon source gas can be disilicone hexachloride (HCD) (Si ₂Cl ₆).If this silicon source gas is HCD, this oxide gas preferably can be H ₂O.Therefore, this hafnium oxide layer and this silicon oxide layer react each other, make to form this hafnium (Hf) silicate layer in substrate.Check then, to determine whether to have formed hafnium silicate layer with required ratio of components.This silicon oxide layer is formed cycle 20 to be repeated Q time and has the metal silicate layer (step 29 of Fig. 1) of required ratio of components until formation in substrate.Counting Q here, is at 1 integer to about 10 scopes.That is to say that silicon/oxide skin(coating) forms the repeat number Q in cycle 20 preferably in 1 time to 10 times scope.

Make according to the preferred embodiments of the invention in the method for metal silicate, must determine or selection number K and Q, it is no more than respectively 10 times.For example, number K can be in the scope of 2-5, and number Q can be 1.More preferably, number K can be 3, and number Q can be 1.If number K are 10 or bigger, form hafnium (Hf) oxide skin(coating) that the cycle 10 forms by hafnium (Hf) oxide skin(coating) and have highly stable chemically stable structure.Yet, form hafnium (Hf) oxide skin(coating) and make that formation hafnium silicate layer is very difficult in the silicon oxide layer process in formation cycle 20 with this type of chemically stable structure.That is to say that because this has hafnium (Hf) oxide skin(coating) of chemically stable structure, this silicon oxide layer can change into and being sticked to respectively on the hafnium oxide layer with chemically stable structure as mentioned above, and/or this silicon oxide layer may not take place form reaction.In addition, if number Q is 10 or bigger, even further supply disilicone hexachloride (HCD) (Si to metal silicate layer ₂Cl ₆) gas, the chemical absorbing layer that contains silicon can not form usually yet.That is to say that even this silica layer formation cycle 20 is surpassed 10 times, other hafnium silicate layer does not further form usually yet.Hafnium silicate layer according to the present invention can be used chemical general formula Hf _xSi _1-xO ₂Expression, wherein, " x " represents the ratio of components of hafnium (Hf) with respect to hafnium+silicon.By controlling several K and the Q of repetition period rightly respectively, can control " x " in the scope of about 0.10-0.95.More preferably, can control " x " in the scope of about 0.65-0.85.That is to say that periodicity K and silicon/oxide periodicity Q by control hafnium/oxide can form the hafnium silicate (Hf with required ratio of components " x " in substrate _xSi _1-xO ₂) layer.

Relevant with this metal silicate layer formation cycle as described, this hafnium silicate layer formation cycle comprises that carrying out K this hafnium oxide layer forms the operation in cycle 10 and comprise the operation of carrying out Q this silicon oxide layer formation cycle 20.Then, check the thickness (step 39 of Fig. 1) of this hafnium silicate layer.This hafnium silicate layer is formed cycleoperation at least once, or repeat until in this substrate, forming hafnium silicate layer with desired thickness.That is to say, repeat K this hafnium oxide layer and form the cycle 10 that next repeat Q this silicon oxide layer and form the cycle 20, such operating sequence is carried out one or many, up to form the hafnium silicate layer with desired thickness on this basalis.

In addition, the invention provides other this hafnium silicate of somewhat similar manufacturing (Hf _xSi _1-xO ₂) layer method.Hereinafter, illustrate certain methods in these other methods with reference to Fig. 1 and 2.

Make in the method for hafnium silicate layer at this type of other, initial or preliminary step comprises the reactor part (step 5) of Fig. 1 that is encased in ALD equipment the suitable semiconductor-based end.

The hafnium oxide layer formation cycle 10 repeats K time in substrate, thereby forms hafnium (Hf) oxide skin(coating) with desired thickness.This hafnium oxide layer formation cycle 10 can comprise independent step: supply hafnium (Hf) source gas (step 11) of Fig. 1, discharge remains in the inside (step 13) of Fig. 1 of unreacted hafnium (Hf) source gas to purify this reactor in the reactor, a kind of oxide gas of supply (step 15) of Fig. 1, and the inside of purification reactor (step 17 of Fig. 1) in this reactor.

Particularly, this hafnium (Hf) source gas is fed to the (step 11) of Fig. 1 in the reactor that has wherein loaded substrate.In one embodiment, this hafnium (Hf) source gas is a kind of chemical general formula HfX that has ₄Material, and X is the element that is selected from the group of being made up of F, Cl, Br and I.In another embodiment, this hafnium source gas is a kind of chemical general formula Hf (NRR ') that has ₄Material, wherein R be selected from by H, Me, Et and ⁱChemical group in the group that Pr forms, and R ' also be selected from by H, Me, Et and ⁱChemical group in the group that Pr forms.In addition, this hafnium (Hf) source gas specifically also can be four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH ₃)] C ₂H ₅] ₄).For example, if supply TEMAH, the burst length that is used for accommodating metal source gas can be about 0.2-2 second.Therefore, the exposed surface along this substrate has formed the chemical absorbing layer that comprises hafnium.After the chemosphere that comprises hafnium (Hf) forms, with the inside (step 13) of Fig. 1 of hafnium (Hf) source gas discharge that remains in the reactor to purify this reactor.In order to discharge this hafnium (Hf) source gas, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, for example argon gas (Ar), helium (He) or nitrogen (N ₂).Then, oxide gas is fed to the (step 15) of Fig. 1 in this reactor.This oxide gas can be to be selected from by oxygen (O ₂), ozone (O ₃), water (H ₂O) and hydrogen peroxide (H ₂O ₂) at least a in the group formed.If TDMAH is used as hafnium (Hf) source gas, this oxide gas is ozone (O preferably ₃).The easy oxidation of ozone may be adhered to the typical impurity on the hafnium.That is to say that this ozone treatment is removed the impurity on the hafnium effectively.Therefore, this chemical absorbing layer and this oxide gas react each other, make to form this hafnium (Hf) oxide skin(coating) in substrate.Then, discharge inside (step 17 of Fig. 1) with remaining in the oxide gas in the reactor and producing gaseous by-product to purify this reactor by the reaction of chemical absorbing layer and oxide gas.In order to discharge this oxide gas and byproduct of reaction, can supply a kind of purge gas to the inside of this reactor.This purge gas generally includes basic inert gasses, for example argon gas (Ar), helium (He) or nitrogen (N ₂).Check then and whether formed hafnium (Hf) oxide skin(coating) with desired thickness.This hafnium (Hf) oxide skin(coating) formation cycle 10 is repeated K time until form hafnium (Hf) oxide skin(coating) (step 19 of Fig. 1) with desired thickness in substrate.Counting K here, is at 1 integer to about 10 scopes.That is to say that hafnium/oxide skin(coating) forms the repeat number K in cycle 10 preferably in 1 time to 10 times scope.

More specifically, according to embodiment of the present invention, this hafnium silicate layer can the general mode identical with the method that reference Fig. 1 and 2 illustrates form.For example, this silicon source gas can use three (dimethylamino) silane (TDMAS) ([(CH ₃)] ₂N] ₃SiH).If this silicon source gas is TDMAS, this oxide gas preferably can be ozone (O ₃).Therefore, this hafnium (Hf) oxide skin(coating) and this silicon oxide layer react each other, to such an extent as to form this hafnium silicate layer.Check then, to determine whether to have formed hafnium silicate layer with required ratio of components.This silicon oxide layer is formed cycle 20 to be repeated Q time and has the metal silicate layer (step 29 of Fig. 1) of required ratio of components until formation in substrate.Counting Q here, is at 1 integer to about 10 scopes.That is to say that silicon/oxide skin(coating) forms the repeat number Q in cycle 20 preferably in 1 time to 10 times scope.

According to the preferred embodiments of the invention, in the method for making metal silicate, must determine or selection number K and Q, it is no more than respectively 10 times.For example, number K can be in the scope of 1-3, and number Q can be 1.More preferably, number K can be 3, and number Q can be 1.If number K are 10 or bigger, form hafnium (Hf) oxide skin(coating) that the cycle 10 forms by hafnium oxide layer and cause having highly stable chemically stable structure.Yet, form hafnium (Hf) oxide skin(coating) and make that formation hafnium silicate layer is very difficult in the silicon oxide layer process in formation cycle 20 with this type of chemically stable structure.That is to say that because this has hafnium (Hf) oxide skin(coating) of chemically stable structure, this silicon oxide layer can change into and being sticked to respectively on the hafnium oxide layer with aforesaid chemically stable structure, and/or this silicon oxide layer formation reaction may not take place.In addition, if number Q is 10 or bigger, even further supply three (dimethylamino) silane (TDMAS) ([(CH to metal silicate layer ₃)] ₂N)] ₃SiH) gas, the extra chemical absorbing layer that contains silicon can not form on the hafnium silicate layer usually yet.That is to say that even this silica layer formation cycle 20 is surpassed 10 times, other hafnium silicate layer does not further form usually yet.Formed hafnium silicate layer can be used chemical general formula Hf according to the present invention _xSi _1-xO ₂Expression, wherein, " x " represents the ratio of components of hafnium (Hf) with respect to hafnium+silicon.Count K and Q by controlling the repetition period rightly respectively, can control " x " in the scope of about 0.10-0.95.More preferably, can control " x " in the scope of about 0.65-0.85.That is to say that periodicity K and silicon/oxide periodicity Q by control hafnium/oxide can form the hafnium silicate (Hf with required ratio of components " x " in substrate _xSi _1-xO ₂) layer.

Relevant with this metal silicate layer formation cycle as described, this hafnium silicate layer formation cycle comprises that carrying out K this hafnium oxide layer forms the operation in cycle 10 and comprise the operation of carrying out Q this silicon oxide layer formation cycle 20.Then, check the thickness (step 39 of Fig. 1) of this hafnium silicate layer.This hafnium silicate layer formation cycle carries out at least once, or repeats until form the hafnium silicate layer with desired thickness in this substrate.That is to say, repeat K this hafnium oxide layer and form the cycle 10 that next repeat Q this silicon oxide layer and form the cycle 20, such operating sequence is carried out one or many, up to form the hafnium silicate layer with desired thickness on this basalis.

Embodiment

Fig. 3 is the curve chart that the different hafnium silicate layer thickness that form on the semiconductor-based end according to embodiments of the invention are described.Horizontal axis P among Fig. 3 represents locating of the semiconductor-based end, and these to locate be to separate each other with 7mm downwards from center, the semiconductor-based end.Vertical axis T among Fig. 3 represents the thickness measured, and thickness unit be _.In 3 embodiment shown in Figure 3, be used for forming in the various process conditions of this hafnium silicate layer, temperature of reactor, sedimentation pressure is identical with the burst length of supply hafnium source gas, is used as comparison with this.Particularly, the temperature of reactor is arranged on 320 ℃, and deposition pressure is arranged on 0.2 torr.In addition, the burst length of supply hafnium source gas is arranged on 0.2 second.

According to Fig. 3, curve A has shown that K is set to 1, and Q is set to 3, and the hafnium silicate layer formation cycle is repeated 40 times result of experiment as described with reference to Fig. 1 and 2.In addition, the hafnium source gas that is used for the hafnium oxide layer formation cycle 10 is TEMAH, and oxide gas is an ozone.In addition, the silicon source gas that is used for the silicon oxide layer formation cycle 20 is HCD, and oxide gas is H ₂O.As a result, as by shown in the curve A among Fig. 3 like that, formed and had the thick hafnium silicate (Hf of about 50_ _xSi _1-xO ₂) layer.

Curve B among Fig. 3 has shown that K is set to 40,, has only been carried out 40 times result of experiment this hafnium oxide layer formation cycle 10 as reference Fig. 1 and 2 is described that is.Curve B has shown the hafnium oxide (HfO that forms as mentioned above ₂) result of thickness of mensuration of layer.Used in addition hafnium source gas is TEMAH, and oxide gas is an ozone.As a result, as by shown in the curve B among Fig. 3 like that, formed and had the thick hafnium oxide (HfO of about 38_ ₂) layer.

Curve C among Fig. 3 has shown the result under such experiment condition, and promptly wherein K is set to 40, that is to say, this hafnium oxide layer formation cycle 10 is carried out 10 times to form hafnium oxide (HfO ₂) layer, then Q also is set to 40, that is to say, this silicon oxide layer formation cycle 20 is carried out 40 times, to have hafnium oxide (HfO ₂) layer the semiconductor-based end on form silicon oxide layer.Curve C has shown the result of the thickness of the mensuration of formed film by the formation step of carrying out the front.In addition, the hafnium source gas that is used for the hafnium oxide layer formation cycle 10 is TEMAH, and oxide gas is an ozone.In addition, the silicon source gas that is used for the silicon oxide layer formation cycle 20 is HCD, and oxide gas is H ₂O.As a result, shown in curve C like that, have the thick hafnium oxide (HfO of 38_ ₂) form without any other film again on the layer.That is to say,,, also do not have extra thickness and be added on this hafnium silicate layer even make this silicon oxide layer form additional carrying out of cycles 20 if aforesaid several K is 40.

According to result embodiment illustrated in fig. 3, by will the repetition period number, promptly count K and Q, control to about 10 or still less aptly, can form hafnium silicate layer best with predetermined thickness.

Fig. 4 to Fig. 6 is according to the present invention, and the correlation curve figure of the thickness of several metal silicate layer that the injection length according to metal source gas changes is described.In Fig. 4 to Fig. 6, changed in the burst length of supply hafnium source gas in reactor.As mentioned above, this hafnium silicate layer formation cycle comprises that carrying out K hafnium oxide layer forms the operation in cycle 10 and carry out the operation that Q time silicon oxide layer forms the cycle 20.Form in hafnium oxide layer that used hafnium source gas is TEMAH in the cycle 10, and oxide gas is an ozone.Form at silicon oxide layer that used silicon source gas is HCD in the cycle 20, and oxide gas is H ₂O.

Fig. 4 is a curve chart, and it has illustrated when the burst length of supply TEMAH is 0.2 second, the thickness distribution of formed hafnium silicate layer.In Fig. 4, substantially the same at the thickness of the hafnium silicate layer of center, the semiconductor-based end and bottom; That is to say that this example has shown the basic uniformly hafnium silicate layer of thickness for about 46_.

Fig. 5 is a curve chart, and it has illustrated when the burst length of supply TEMAH is 0.1 second, the thickness distribution of formed hafnium silicate layer.Different with the result of Fig. 4, the thickness of hafnium silicate layer is almost even at center, the semiconductor-based end, but significantly reduces towards the bottom at this semiconductor-based end.Particularly, the thickness of this hafnium silicate layer descends fast at the regional of curve chart with letter (E) sign, and it is to be positioned from the about 70mm in the center at the semiconductor-based end.

Fig. 6 is a curve chart, and it has illustrated when the burst length of supply TEMAH is 0.05 second, the thickness distribution of formed hafnium silicate layer.Though the thickness of hafnium silicate layer is somewhat identical at center, the semiconductor-based end, reduce apace and substantially towards the bottom at this semiconductor-based end.Particularly, the thickness of this hafnium silicate layer descends fast in the curve chart zone with letter (E) sign, and it is to be positioned from the about 42mm in the center at the semiconductor-based end.Believe it is for these results' explanation, this TEMAH can not be fed to fully the bottom at the semiconductor-based end because the burst length of supply TEMAH is too short.

As from shown in the result of Fig. 4 to 6, the burst length of supply TEMAH preferably is arranged on about 0.2 second or more in these examples.The burst length of for example supplying this TEMAH can be arranged in the about 0.2-2 scope of second.

Fig. 7 be explanation in the process of metal silicate layer formed according to the present invention, deposit thickness is the curve chart that how changes according to the injection rate of metal source gas and silicon source gas; Horizontal axis F represents the injection rate of source gas in Fig. 7, and vertical axis T represents deposit thickness.

With reference to Fig. 7, the varied in thickness of the metal silicate layer that forms according to the increase of source gas injection rate shows with curve S.Particularly, curve S has non-saturated region, and the thickness of the metal silicate layer that forms in substrate in this zone increases with the increase of the supply of source gas.Therefore in addition, this curve S also has the saturation region, and the thickness of the metal silicate layer that forms in substrate in this zone reaches plateau, does not further increase with the further increase of the supply of source gas.Thereby, according to the present invention, can be by the supply of Controlling Source gas aptly, at least in the unsaturation zone of curve, thereby control forms the deposit thickness of metal silicate layer, and and then has also controlled the ratio of components of this metal silicate layer.

For example, in order to form metal silicate layer with high metallic element ratio of components, supply this metal source gas with the amount that is positioned at curve S zone of saturation (representing the maximum of the metal that this metal silicate layer can contain), and supply this silicon source gas with the amount in the unsaturation zone (expression is lower a little than the maximum of the silicon that metal silicate layer can contain) that is positioned at curve.On the contrary, in order to form metal silicate layer with high element silicon ratio of components, amount with the unsaturation zone (maximum that is less than metal) that is positioned at curve S is supplied this metal source gas, and supplies this silicon source gas with the amount of the zone of saturation (maximum of silicon) that is positioned at curve.

Fig. 8 to Figure 11 is the hafnium silicate (Hf that explanation is deposited according to the present invention _xSi _1-xO ₂) layer x-ray photoelectron spectroscopy (XPS) analysis result curve chart.The horizontal axis M of Fig. 8 to 11 represents the sputtering time of XPS, and its linear module is minute, and vertical axis A represents atomic concentration, and its unit is percentage (%).

In the various process conditions that form the hafnium silicate layer, be separately positioned on 320 ℃ and 0.2 torr as the temperature and the deposition pressure of the reactor among Fig. 8 to Figure 11.The hafnium source gas that is used for the hafnium oxide layer formation cycle 10 is TEMAH, and oxide gas is an ozone.In addition, the silicon source gas that is used for the silicon oxide layer formation cycle 20 is HCD, and oxide gas is H ₂O.The formation cycle of complete hafnium silicate layer has carried out respectively 80 times in Fig. 8 to Figure 11.As mentioned above, each complete hafnium silicate layer formation method comprises that carrying out K hafnium oxide layer forms the operation in cycle 10 and carry out the operation that Q time silicon oxide layer forms the cycle 20.In Fig. 8 to 11, K is set to different values with Q.

In order to remove in XPS analysis the possibility of surface contamination in the contingent sample, after the test result that begins back 2 minutes to 14 minute time period inner analysis points from sputter and provided is handled, be considered to " valid period " D part, and these results are used for analyzing hafnium silicate (Hf _xSi _1-xO ₂) layer ratio of components.In valid period D, the ratio of components of two kinds of common surface contaminant carbon (C) and chlorine (Cl) such as Fig. 8 to 11 are depicted as 0.5% and still less.

Fig. 8 has shown formed hafnium silicate (Hf _xSi _1-xO ₂) the XPS analysis result of layer, wherein K=1, Q=3.Based on valid period D, formed hafnium silicate (Hf _xSi _1-xO ₂) layer shown the composition of Hf=17.8, Si=17.9, O=63.8.In this hafnium silicate layer, hafnium is 0.50 ± 0.03 with respect to the ratio of components " x " of hafnium+silicon.

Fig. 9 has shown formed hafnium silicate (Hf _xSi _1-xO ₂) the XPS analysis result of layer, wherein K=1, Q=1.Based on valid period D, formed hafnium silicate (Hf _xSi _1-xO ₂) layer shown the composition of Hf=21.9, Si=14.3, O=62.2.In this hafnium silicate layer, hafnium is 0.61 ± 0.04 with respect to the ratio of components " x " of hafnium+silicon.

Figure 10 has shown formed hafnium silicate (Hf _xSi _1-xO ₂) the XPS analysis result of layer, wherein K=3, Q=1.Based on valid period D, formed hafnium silicate (Hf _xSi _1-xO ₂) layer shown the composition of Hf=29.2, Si=9.8, O=58.7.In this hafnium silicate layer, hafnium is 0.75 ± 0.03 with respect to the ratio of components " x " of hafnium+silicon.

Figure 11 has shown formed hafnium silicate (Hf _xSi _1-xO ₂) the XPS analysis result of layer, wherein K=5, Q=1.Based on valid period D, formed hafnium silicate (Hf _xSi _1-xO ₂) layer shown the composition of Hf=30.7, Si=8.0, O=60.3.In this hafnium silicate layer, hafnium is 0.80 ± 0.05 with respect to the ratio of components " x " of hafnium+silicon.

From the XPS analysis result of front as seen, in the hafnium silicate layer, hafnium can be controlled by control K and Q value aptly in the hafnium silicate formation method of Fig. 1 and Fig. 2 with respect to the ratio of components of hafnium+silicon.Have been found that if metallic element, the ratio of components of hafnium is higher relatively, the dielectric constant of this layer increases, and the flowability of charge carrier reduces.On the contrary, have been found that if with respect to element silicon, metallic element, the ratio of components of hafnium is lower, and the flowability of this layer charge carrier increases, and dielectric constant reduces.Therefore, if control K and Q value aptly, can make the performance of resulting dielectric layer be optimised selection to be used for specific application.

Figure 12 is a curve chart, and it has illustrated how the thickness of hafnium silicate layer repeats to form the quantity in cycle according to the present invention and increase.The horizontal axis C of Figure 12 represents that hafnium silicate forms the quantity of the repetition period in cycle, and vertical axis T represents the mensuration thickness of resulting hafnium silicate layer.The hafnium source gas that is used for the hafnium oxide layer formation cycle 10 for this example is TEMAH, and oxide gas is an ozone, and K=1.In addition, the silicon source gas that is used for the silicon oxide layer formation cycle 20 is HCD, and oxide gas is H ₂O, and Q=3.

With reference to Figure 12, draw that thereby curve is found according to the increase of the formation periodicity of the hafnium silicate layer that repeats and linear increasing according to the thickness of hafnium silicate layer to forming periodicity, and the corresponding linear equation can be determined: T=4.635+1.01797C as follows.That is to say that the thickness of hafnium silicate layer can accurately be controlled by the formation periodicity of controlling the hafnium silicate layer that repeats.It will be understood by those skilled in the art that difference combination, layer thickness is interrelated with forming periodicity, can determine slightly different linear equation for the technological parameter of manipulating in the present invention.

Figure 13 is a curve chart, and it illustrates when different hafnium silicate layer formed according to the present invention is used in the MOS transistor, the curve chart of the variation degradation characteristic of leakage current.The horizontal axis S of Figure 13 represents the stress time that is applied to MOS transistor with chronomere's scale second.Vertical axis in Figure 13 curve (Δ l _d) expression leakage current the deterioration rate, with percentage (%) scale.The deterioration rate of leakage current can be calculated as the ratio of the difference of the drain saturation current behind initial drain saturation current and the certain stress time with respect to initial drain saturation current.

The MOS transistor that is used for the present invention experiment is to use the template of the length L of width W with 10um and 0.13um to make.In addition, the gate dielectric of several MOS transistor is to be that the thick different hafnium silicate layer of 30_ forms by each layer.As see figures.1.and.2 described, each complete hafnium silicate layer formation method comprises into K the operation that capable hafnium oxide layer forms the operation in cycle 10 and carries out Q silicon oxide layer formation cycle 20.In addition, form in hafnium oxide layer that used hafnium source gas is TEMAH in the cycle 10, and oxide gas is an ozone.In addition, form at silicon oxide layer that used silicon source gas is HCD in the cycle 20, and oxide gas is H ₂O.For each gate dielectric, K is set to different values with Q.

As for the bias condition that is used for MOS transistor in the embodiments of the invention, grid voltage Vg is that 3.0V and electric leakage potential difference Vd are 3.0V.

With reference to Figure 13, curve HS31 has shown the degradation characteristic with respect to the hafnium silicate layer leakage current that forms under the condition of K=3, Q=1.Similarly, curve HS51 has shown the degradation characteristic with respect to the hafnium silicate layer leakage current that forms under the condition of K=5, Q=1.Curve HS11 has shown the degradation characteristic with respect to the hafnium silicate layer leakage current that forms under the condition of K=1, Q=1.Curve HS13 is illustrated in the hafnium silicate layer that forms under K=1, the Q=3 condition.

As shown in Figure 13, all embodiment of the present invention demonstrate good leakage current degradation characteristic.Especially, have been found that with result and compare by the hafnium silicate layer of other curve representation, best by the degradation characteristic of the leakage current of the hafnium silicate layer of curve HS31 (K=3, Q=1) expression.With reference to the XPS analysis result of Figure 10, by the hafnium silicate (Hf that K=3, Q=1 form is set _xSi _1-xO ₂) layer has the ratio of components " x " of hafnium with respect to hafnium+silicon 0.75 ± 0.03.That is to say, compare to have the hafnium silicate (Hf of ratio of components " x "=0.75 ± 0.03 with hafnium silicate layer with other ratio of components _xSi _1-xO ₂) layer demonstrates relatively better leakage current degradation characteristic.

Figure 14 is a curve chart, the variation degradation characteristic of its explanation different embodiment according to the subject invention mutual conductance (Gm) and threshold voltage (Vth).In the curve chart of Figure 14, horizontal axis (KQ) is illustrated in the different K that the hafnium silicate layer used in the formation cycle: the Q ratio.For example, the point of horizontal axis (KQ) means K=5 and Q=1 at 5: 1.In the curve chart of Figure 14, first (left side) vertical axis (Δ Gm/Gm) expression is with the deterioration rate of the mutual conductance of percentage (%) expression.The deterioration rate of mutual conductance can be calculated as initial mutual conductance and the difference between the mutual conductance behind 1000 seconds the stress time ratio with respect to initial mutual conductance.The flowability of the charge carrier in this mutual conductance and the dielectric substrate is linear direct ratio.In the curve chart of Figure 14, second (right side) vertical axis (Δ Vth) expression is poor with the threshold voltage of volt (V) scale.The difference of this threshold voltage can be calculated as initial threshold voltage and poor between the threshold voltage of measuring behind 1000 seconds the stress time.

The MOS transistor that is used for the embodiment of the invention is made under the essentially identical process conditions of aforesaid Figure 13.In addition, as for the bias condition that is used for MOS transistor in the embodiments of the invention, grid voltage Vg is that 3.0V and electric leakage potential difference Vd are 3.0V.

The curve G of Figure 14 represents the degradation characteristic of mutual conductance.With reference to the point on the data point on the curve G and the relevant horizontal axis KQ, can find to compare with other example, the deteriorate performance of optimal mutual conductance is by obtaining by the formed hafnium silicate layer of K=5 and Q=1 is set.

The curve V of Figure 14 represents the degradation characteristic of threshold voltage.With reference to the point on the data point on the curve V and the relevant horizontal axis KQ, can find to compare with other example, the deteriorate performance of the threshold voltage of wishing most is by obtaining by the formed hafnium silicate layer of K=3 and Q=1 is set.

Figure 15 is a curve chart, and it has illustrated that when different hafnium silicate layers formed according to the present invention are applied to making different MOS transistor hot carrier is injected the different duration characteristic that (HCI) can reach.The inverse of the electric leakage potential difference of the horizontal axis of curve chart (1/Vd) expression MOS transistor among Figure 15.The vertical axis of curve chart (L) expression is with the duration of (sec.) scale second among Figure 15.

The MOS transistor that is used for embodiments of the invention is to make under the essentially identical process conditions of Figure 13 as described above.In addition, as for the bias condition that is used for MOS transistor in the embodiments of the invention, grid voltage Vg is that 3.0V and electric leakage potential difference Vd are 3.0V.

With reference to Figure 15, HS31 has shown the duration characteristic of injecting (HCI) under the condition of K=3, Q=1 with respect to the hafnium silicate layer hot carrier that forms.Similarly, curve HS51 has shown the duration characteristic with respect to the HCI of the hafnium silicate layer that forms under the condition of K=5, Q=1.Curve HS11 has shown the duration characteristic with respect to the hafnium silicate layer HCI that forms under the condition of K=1, Q=1.

As shown in Figure 15, all embodiment of the present invention demonstrate the duration characteristic of good HCI.Especially, and compare, reveal this best class feature by the duration property list of the HCI of the hafnium silicate layer of curve HS31 (K=3, Q=1) expression by other curve.With reference to the XPS analysis result of Figure 10, under K=3, Q=1 condition, form hafnium silicate (Hf _xSi _1-xO ₂) layer, thus hafnium with respect to the ratio of components " x " of hafnium+silicon in 0.75 ± 0.03 scope.That is to say, compare to have the hafnium silicate (Hf of ratio of components " x "=0.75 ± 0.03 with hafnium silicate layer with other ratio of components _xSi _1-xO ₂) layer demonstrates the duration characteristic of better HCI.

Figure 16 is a curve chart, and its explanation is by the various durations characteristic of the positive bias temperature instability (PBTI) that different embodiments of the invention showed.Horizontal axis in the curve chart of Figure 16 (Vg) the expression transistorized grid voltage Vg of nMOS of volt (V) scale.The vertical axis of curve chart (L) expression is with the duration of (sec.) scale second among Figure 16.

The nMOS transistor that is used for the present invention experiment is to use the template of the length L of width W with 10 μ m and 1 μ m to make.In addition, the transistorized gate dielectric of several nMOS is to be that the thick different hafnium silicate layers of 30_ form by each layer.As see figures.1.and.2 described, each complete hafnium silicate layer formation method comprises carries out the operation that K hafnium oxide layer forms the operation in cycle 10 and carry out Q silicon oxide layer formation cycle 20.In addition, form in hafnium oxide layer that used hafnium source gas is TEMAH in the cycle 10, and oxide gas is an ozone.In addition, form at silicon oxide layer that used silicon source gas is HCD in the cycle 20, and oxide gas is H ₂O.For each gate dielectric, K is set to different values with Q.

In an embodiment of the present invention, be applied to the transistorized electric leakage potential difference of nMOS Vd be set to identical, i.e. 50mV.In addition, the temperature of positive bias temperature instability (PBTI) condition is 125 ℃.

With reference to Figure 16, HS31 has shown with respect to the hafnium silicate layer PBTI duration characteristic that forms under the condition of K=3, Q=1.Similarly, curve HS51 has shown the PBTI duration characteristic with respect to the hafnium silicate layer that forms under the condition of K=5, Q=1.Curve HS11 has shown with respect to the hafnium silicate layer PBTI duration characteristic that forms under the condition of K=1, Q=1; And curve HS13 has shown with respect to the hafnium silicate layer PBTI duration characteristic that forms under the condition of K=1, Q=3.

As shown in Figure 16, all embodiment of the present invention demonstrate good PBTI duration characteristic.Especially, and compare, reveal this best class feature by the PBTI duration property list of the hafnium silicate layer of curve HS31 (K=3, Q=1) expression by other curve.With reference to the XPS analysis result of Figure 10, under K=3, Q=1 condition, form hafnium silicate (Hf _xSi _1-xO ₂) layer, thus hafnium with respect to the ratio of components " x " of hafnium+silicon in 0.75 ± 0.03 scope.That is to say, compare to have the hafnium silicate (Hf of ratio of components " x "=0.75 ± 0.03 with hafnium silicate layer with other ratio of components _xSi _1-xO ₂) layer demonstrates better PBTI duration characteristic.

According to the present invention as described above, a complete hafnium silicate layer formation cycle comprises that carrying out K hafnium oxide layer forms the operation in cycle and carry out the operation that Q time silicon oxide layer forms the cycle.Number K and number Q can be the integers in the 1-10 scope.In metal silicate layer, can repetition period in each silicate layer formation cycle be counted K and number Q control the ratio of components of metal with respect to silicon by suitably controlling respectively.In addition, can control the thickness of metal silicate layer by the periodicity of suitably controlling the metal silicate layer formation cycle that repeats.Therefore, use ALD technology according to the present invention can make metal silicate layer with required ratio of components and required uniform thickness.

It is respectively korean patent application 2004-0034431 number of on May 14th, 2004 and application on November 30th, 2004 and 2004-0099511 number priority that the application requires, be incorporated herein by reference in full in this disclosure, as all setting forth at this with these two parts of applications.The application also requires the priority based on the U.S. Provisional Application sequence number 60/618,106 of application on October 13rd, 2004.

Claims

1. method of using atom layer deposition process to make metal silicate layer in substrate, described method comprise the step of order:

(a) substrate is loaded into reactor;

(b) under reaction condition, supply contains the metal source gas of required metal in the reactor with substrate, to form the first chemical absorbing layer that comprises required metal in substrate;

(c) under reaction condition, in reactor, supply oxide gas, make itself and the first chemical absorbing layer reaction that comprises required metal, in substrate, to form the metal oxide layer that comprises required metal;

(d) sequentially repeat step (b) and (c) K time;

(e) under reaction condition, to this reactor supply silicon source gas, on suprabasil metal oxide layer, to form the second chemical absorbing layer that comprises silicon;

(f) under reaction condition, in reactor, supply oxide gas, itself and this metal oxide layer is reacted, to form metal silicate layer with the second chemical absorbing layer that comprises silicon;

(g) sequentially repeat step (e) and (f) Q time; And

(h) sequentially carrying out step (b), (c), (d), (e), (f) and operation (g) at least once, have the metal silicate layer of desired thickness thereby form, is 2 at least one of among its intermediate value K and the Q.

2. method according to claim 1, it also comprises step:

(c) is preceding in step, after each step (b) step, discharges the unreacted metal source gas remain in the reactor to purify the inside of this reactor;

(d) is preceding in step, after each step (c) step, discharges the unreacted oxide gas remain in the reactor and byproduct of reaction to purify the inside of this reactor;

(f) is preceding in step, after each step (e) step, discharges the unreacted oxide gas remain in the reactor to purify the inside of this reactor;

(g) is preceding in step, after each step (f) step, discharges the unreacted oxide gas remain in the reactor and byproduct of reaction to purify the inside of this reactor.

3. method according to claim 1, wherein the value of K or Q is in the scope of 1-10.

4. method according to claim 1, wherein the value of K is in the scope of 2-5, and the value of Q is 1.

5. method according to claim 1, wherein K be 3 and Q be 1.

6. method according to claim 1, wherein said reaction condition comprise that the temperature of reactor is in about 250 ℃-600 ℃ scope.

7. method according to claim 1, wherein this metal source gas is to have chemical general formula MX ₄Material, wherein M is selected from a kind of in the group of being made up of Hf, Zr and Ti, and X is selected from a kind of in the group of being made up of F, Cl, Br and I.

8. method according to claim 1, wherein this source metal other be to have chemical general formula M (NRR ') ₄Material, wherein M is selected from a kind of in the group of being made up of Hf, Zr and Ti; R be selected from by H, Me, Et and ⁱA kind of in the group that Pr forms; And R ' be selected from by H, Me, Et and ⁱA kind of in the group that Pr forms.

9. method according to claim 1, wherein this source metal is four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH ₃) C ₂H ₅] ₄).

10. method according to claim 9, the burst length of wherein supplying this metal source gas is in about 0.2-2 scope of second.

11. method according to claim 1, wherein this oxide gas is at least a being selected from by H ₂O, O ₃, O ₂And H ₂O ₂At least a in the group of forming.

12. method according to claim 1, wherein this silicon source gas is to have chemical general formula Si _nX ' 2 _N+2O _N-1Material, wherein n is the number of 1-4, and X ' is selected from a kind of in the group of being made up of NCO, F, Cl, Br and I.

13. method according to claim 1, wherein this silicon source gas is to have chemical general formula Si _nX ' _2n+2O _N-1Material, wherein n is the number of 2-5, and X ' is selected from by NCO, F, Cl, a kind of in the group that Br and I form.

14. method according to claim 1, wherein this silicon source gas is to have chemical general formula SinX " _n(NRR ') _4-nMaterial, wherein n is the number of 0-3; X " be to be selected from a kind of in the group of forming by H, F, Cl, Br and I; R be selected from by H, Me, Et and ⁱA kind of in the group that Pr forms; And R ' be selected from by H, Me, Et and ⁱA kind of in the group that Pr forms.

15. method according to claim 1, wherein this silicon source gas is to have chemical general formula NH _n(SiR " ₃) _3-nMaterial, wherein n is the number of 0-2; And R " be selected from by H, F, Cl, Br, I, Me, Et and ⁱA kind of in the group that Pr forms.

16. method according to claim 1, wherein this silicon source gas is to have chemical general formula SiSX ₂Material, wherein X is selected from a kind of in the group of being made up of F, Cl, Br and I.

17. method according to claim 1, wherein this silicon source gas is disilicone hexachloride (HCD) (Si ₂Cl ₆), or three (dimethylamino) silane (TDMAS) ([(CH ₃) ₂N] ₃SiH).

18. method according to claim 1 is wherein at metal silicate (M _xSi _1-xO ₂) layer in metallic element add the ratio of components x of silicon in the scope of about 0.10-0.95 with respect to metal.

19. method according to claim 1 is wherein at metal silicate (M _xSi _1-xO ₂) layer in metal add the ratio of components x of silicon in the scope of about 0.65-0.85 with respect to metal.

20. a method of using atom layer deposition process to make the hafnium silicate layer in substrate, described method comprise the step of order:

(a) substrate is loaded into reactor;

(b) under reaction condition, in reactor, supply four (ethyl methylamino) hafnium (TEMAH) (Hf[N (CH with substrate ₃) C ₂H ₅] ₄) gas, in substrate, to form the first chemical absorbing layer that comprises hafnium (Hf);

(c) under reaction condition, in reactor, supply oxide gas, make itself and the first chemical absorbing layer reaction that comprises hafnium (Hf), in substrate, to form hafnium (Hf) oxide skin(coating);

(d) sequentially repeat step (b) and (c) K time;

(e) under reaction condition, to this reactor supply disilicone hexachloride (HCD) (Si ₂Cl ₆) gas, on suprabasil hafnium (Hf) oxide skin(coating), to form the second chemical absorbing layer that comprises silicon;

(f) under reaction condition, in reactor, supply oxide gas, itself and this hafnium (Hf) oxide skin(coating) is reacted, to form hafnium silicate (Hf with the second chemical absorbing layer that comprises silicon _xSi _1-xO ₂) layer;

(g) sequentially repeat step (e) and (f) Q time; And

(h) sequentially carrying out step (b), (c), (d), (e), (f) and operation (g) at least once, thereby form the hafnium silicate layer with desired thickness, is 2 at least one of among its intermediate value K and the Q.

21. method according to claim 20, it also comprises step:

(c) is preceding in step, after each step (b) step, discharges the unreacted TEMAH gas remain in the reactor to purify the inside of this reactor;

(f) is preceding in step, after each step (e) step, discharges the unreacted HCD gas remain in the reactor to purify the inside of this reactor; And

22. method according to claim 20, wherein the value of K or Q is in the scope of 1-10.

23. method according to claim 20, wherein the value of K is in the scope of 2-5, and the value of Q is 1.

24. method according to claim 20, wherein K be 3 and Q be 1.

25. method according to claim 20, wherein said reaction condition comprise that the temperature of reactor is in about 250 ℃-600 ℃ scope.

26. method according to claim 20, the burst length of wherein supplying this TEMAH gas is in about 0.2-2 scope of second.

27. method according to claim 20, wherein this oxide gas is to be selected from by H ₂O, O ₃, O ₂And H ₂O ₂The group of forming at least a.

28. method according to claim 20 is wherein at hafnium silicate (Hf _xSi _1-xO ₂) layer in hafnium (Hf) element add the ratio of components x of silicon in the scope of about 0.10-0.95 with respect to hafnium.

29. method according to claim 20 is wherein at hafnium silicate (Hf _xSi _1-xO ₂) layer in hafnium (Hf) element add the ratio of components x of silicon in the scope of about 0.65-0.85 with respect to hafnium.

30. a method of using atom layer deposition process to make the hafnium silicate layer in substrate, described method comprise the step of order:

(a) substrate is loaded into reactor;

(d) sequentially repeat step (b) and (c) K time;

(e) under reaction condition, to this reactor supply three (dimethylamino) silane (TDMAS) ([(CH ₃) ₂N] ₃SiH) gas is to form the second chemical absorbing layer that comprises silicon on suprabasil hafnium (Hf) oxide skin(coating);

(g) sequentially repeat step (e) and (f) Q time; And

31. method according to claim 30, it also comprises step:

(f) is preceding in step, after each step (e) step, discharges the unreacted TDMAS gas remain in the reactor to purify the inside of this reactor; And

32. method according to claim 30, wherein the value of K or Q is in the scope of 1-10.

33. method according to claim 30, wherein the value of K is in the scope of 1-3, and the value of Q is 1.

34. method according to claim 30, wherein said reaction condition comprise that the temperature of reactor is in about 250 ℃-600 ℃ scope.

35. method according to claim 30, the burst length of wherein supplying this TEMAH gas is in about 0.2-2 scope of second.

36. method according to claim 30, wherein this oxide gas is to be selected from by H ₂O, O ₃, O ₂And H ₂O ₂The group of forming at least a.

37. method according to claim 30 is wherein at hafnium silicate (Hf _xSi _1-xO ₂) layer in hafnium (Hf) element add the ratio of components x of silicon in the scope of about 0.10-0.95 with respect to hafnium.

38. method according to claim 30 is wherein at hafnium silicate (Hf _xSi _1-xO ₂) layer in hafnium (Hf) element add the ratio of components x of silicon in the scope of about 0.65-0.85 with respect to hafnium.