WO2003012851A2

WO2003012851A2 - Method of etching ferroelectric layers

Info

Publication number: WO2003012851A2
Application number: PCT/US2002/024346
Authority: WO
Inventors: Hideyuki Yamauchi
Original assignee: Applied Materials, Inc.
Priority date: 2001-07-31
Filing date: 2002-07-31
Publication date: 2003-02-13
Also published as: US20030047532A1; TW565886B; WO2003012851A3; JP2003059906A

Abstract

A method of etching a ferroelectric layer comprises etching a ferroelectric layer using boron trichloride gas and at least one auxiliary gas selected from the group consisting of a carbon-containing gas and a nitrogen-containing gas. The carbon-containing gas may include CHF3 or C2H4. The nitrogen-containing gas may include N2 or NF3. The method reduces side etching of ferroelectric layers, and in particular, PZT-based ferroelectric layers and thereby improves electrical performance and reliability of devices made therefrom.

Description

METHOD OF ETCHING FERROELECTRIC LAYERS

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to co-pending Japanese patent application number 2001 -232528, filed in Japan on July 31 , 2001.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention generally relates to etching ferroelectric materials and, more particularly, to the use of carbon-containing gases and nitrogen-containing gases to etch ferroelectric layers.

Description of the Related Art

Lead zirconate titanate (PZT), a ferroelectric oxide material, is often used for memory cell applications. Various methods for processing PZT have been discussed in the art. In order to etch PZT, process gases including boron trichloride (BCI₃) gas and argon (Ar) gas have been used. However, using boron trichloride (BCI₃) gas and argon (Ar) gas to etch PZT layers has been found to result in etching the side of the PZT layer. This side-etching may result in various problems in subsequent processing steps. For example, when forming an insulating layer on the PZT layer, side-etching may result in unsatisfactory step coverage of the insulating layer. Furthermore, variations in side-etching of the PZT layer may result in memory cells formed therefrom having different capacitance, thereby causing unreliable electrical performance. Therefore, a need exists to reduce side-etching in PZT layers. SUMMARY OF THE INVENTION

Embodiments of the present invention generally relate to a method of etching /a PZT-based ferroelectric layer with limited side etching. In one embodiment of the invention, an etching process comprises etching a PZT-based ferroelectric layer with a process gas, wherein the process gas includes boron trichloride gas and at least one auxiliary gas selected from the group consisting of a carbon-containing gas e.g., hydroflurocarbon and a nitrogen-containing gas. The at least one auxiliary gas may comprise, for example, CHF₃, C₂H₄₎ N₂, NF₃, or combinations thereof. The process gas may further comprise argon. The use of an auxiliary gas limits side etching. In another embodiment of the invention, a method of forming a capacitor having dielectric portions disposed between first electrodes and second electrodes is provided. The process comprises etching the first conductive layer to form first electrodes. The PZT-based ferroelectric layer is then etched with a process gas comprising boron trichloride and at least one auxiliary gas selected from the group consisting of a carbon-containing gas and a nitrogen-containing gas to form dielectric portions. The second conductive layer is then etched to form second electrodes.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features, advantages and objects of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.

It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

Fig. 1a-Fig. 1j are cross-sectional views of a substrate during various stages of processing according to one embodiment of the present invention;

Fig. 2(a) depicts a schematic cross-sectional diagram of a dielectric portion formed using embodiments of the invention described herein. Fig. 2(b) depicts a schematic diagram showing the cross section of the PZT layer etched using a process gas composed of only BCI₃ gas and Ar gas;

Fig. 3 is a schematic diagram showing an exemplary plasma etching apparatus that may be used to practice embodiments of the invention described herein;

Fig. 4 is a circuit diagram showing a capacitor comprising a memory cell formed by the etching process according to embodiments of the invention described herein; and

Fig. 5 is a graph depicting a hysteresis phenomenon of a ferroelectric material that may be etched using embodiments of the invention described herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Embodiments described herein relate to a method of etching a PZT-based ferroelectric layer. Fig. 1a-Fig. 1j are cross-sectional views of a substrate during various stages of processing according to one embodiment of the present invention. As shown in Fig. 1 a, a conductive layer such as platinum (Pt) layer 3 is formed on a substrate 2. The substrate 2 may be, for example, a semiconductor substrate such as a silicon (Si) wafer, a Si wafer having an insulating layer such as a silicon oxide (Si0₂) layer formed thereon, or a Si wafer upon which a partially completed semiconductor integrated circuit has been fabricated. The method employed for forming Pt layer 3, may be, for example, a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method. As shown in Fig. 1 b, a ferroelectric layer such as a PZT layer 4 is formed on the first Pt layer 3. The PZT layer 4 may be formed by a physical vapor deposition (PVD) process or a sol-gel process. Next, as shown in Fig. 1 c, a conductive layer such as an iridium (Ir) layer 5 is formed on the PZT layer 4, using a deposition method such as, for example, chemical vapor deposition (CVD) or PVD. As a result, a multi-layer film composed of the platinum (Pt) layer 3, the PZT layer 4 and the Ir layer 5 is formed.

Subsequently, in order to form hard masks on the multi-layer film, an Si0₂ layer 6 is formed on the Ir layer 5, as shown in Fig. 1d. The Si0₂ layer 6 may be formed by, for example, a plasma CVD method using tetraethyl orthosilicate (TEOS) and oxygen (0₂) gas as raw materials. Thereafter, a resist layer (not shown) is applied on the Si0₂ layer 6, and the resist layer is then exposed via a photomask having a predetermined pattern. As shown in Fig. 1e, resist masks 7 are thereby formed. The resist masks 7 are then used to etch the Si0₂ layer 6, as shown in Fig. 1f. This etching may be performed using, for example, a plasma etching apparatus appropriate for Si0₂ layer etching. A process gas including, for example, Cl₂ and CF , may be used to perform the Si0₂ layer etching. After etching the Si0₂ layer, the resist mask 7 is removed by ashing. As a result, hard masks 8 are formed as shown in Fig. 1g. After the formation of the hard masks 8, the substrate 2 is placed in an etching chamber of a predetermined plasma etching apparatus. After the substrate 2 is placed in the etching chamber, a substrate support temperature is maintained within a range not lower than 250 degrees and not higher than 400 degrees. The temperature may be, for example, 310 degrees. After the temperature of the substrate 2 becomes stable at 310 degrees, process gas is introduced into the etching chamber. The portions of the Ir layer 5 that are not covered by the hard masks 8 are etched, and the portions of the Ir layer 5 that are covered by hard masks 8 are unetched, thus forming upper Ir electrodes 9, as shown in Fig. 1h. The process gas used to etch the IR layer 5 may include chlorine (Cl₂) gas and oxygen (0₂) gas.

After the Ir electrodes 9 are formed, the PZT layer 4 is etched in the same etching chamber as used to etch the Ir layer 5. The etching of the PZT layer 4 may be performed at a substrate temperature substantially the same as that during the etching of the Pt layer 3. A process gas comprising BCI₃ gas, Ar gas and a carbon- containing gas such as a fluorohydrocarbon, e.g., CHF₃ may be used to etch the PZT layer 4. Process conditions useful for etching the PZT layer 4 are, for example, a flow rate of BCI₃ of 40 standard cubic centimeters per minute (seem), a flow rate of Ar of 90 seem, a flow rate of CHF₃ of 5 seem, a chamber pressure of about 2.0Pa (15mTorr), a power output of for plasma generation of 1500W, a substrate bias output of 150W, and a substrate temperature of 310 degrees. As a result of the etching of PZT layer 4, portions of the PZT layer 4 that are not covered by hard mask^'s 8 and Ir electrodes 9 are removed, thereby forming dielectric portions 10 as indicated in Fig. 1f. Subsequently, the supply of BCI₃ gas and Ar gas is terminated, and Cl₂ gas and 0₂ are supplied to etch the Pt layer 3. Upon etching the Pt layer 3, upper Pt electrodes 11 are formed, and the formation of a ferroelectric capacitor 1 is completed, as shown in Fig. 1j. The hard masks 8 may remain in the semiconductor device without being removed. Alternatively, the hard masks 8 are removed by etching the hard masks 8 with a hydrofluoric acid solution.

Fig. 2a depicts a schematic cross-sectional diagram of the dielectric portion

10 formed using the method described above. This cross-sectional diagram was prepared on the basis of a SEM photograph. The sidewall of dielectric portion 10 composed of PZT is substantially uniform, thereby indicating that side-etching has been sufficiently prevented using the above-described method.

For the purpose of comparison, Fig. 2b depicts a schematic cross-sectional diagram of the dielectric portion 10 formed from a PZT layer formed on an Ru layer 30. The dielectric portion 10 was etched without supplying CHF₃. As shown in Fig. 2b, an overhang is formed on a sidewall 40 of the PZT layer 4. The presence of the overhang reveals that significant side-etching occurred during the etching of the PZT layer 4.

Without wishing to be bound by any particular theory or mechanism, the inventors believe that the side-etching of the PZT layer 4 is prevented by the carbon, specifically, organic substances such as carbon-containing fragments generated from the decomposition of CHF₃ that adhere to the sidewall 40 of the PZT layer 4.

The flow rate of the carbon-containing gas, such as CHF₃, supplied to the chamber is, in an illustrative embodiment, not less than 1 seem. When the flow rate of the carbon-containing gas is less than 1 seem, prevention of the side-etching effect may be insufficient because the carbon or the organic substances generated from the decomposition of, for example, CHF₃, cannot cover the sidewall sufficiently. Furthermore, if the flow rate of carbon-containing gas is greater than 10 seem, the material adhering to the sidewall 40 may be too thick and peel off, thus failing to prevent side-etching.

Furthermore, the carbon-containing gas may be supplied at a flow rate that is not less than 1 % by mole with respect to a total flow rate of the process gas supplied during the etching. It is believed that if the ratio of the carbon-containing gas to BCI₃ gas is too small, the side-etching cannot be prevented due to an insufficient amount of material adhering to the sidewall. It is also believed that if the carbon-containing gas is supplied in a concentration greater than 10% by mole, the carbon-containing gas would inhibit the etching of the PZT layer 4.

In an alternative embodiment of the invention, the process gas used to etch the PZT layer 4 comprises a nitrogen-containing gas such as N₂. The flow rate of the N-containing gas may be between 1 standard cubic centimeter per second (seem) and 10 seem. Furthermore, the ratio of the N-containing gas to the total process gas flow rate may be between 1 % by mole and 10% by mole. Without wishing to be bound by any particular theory or mechanism, the inventors believe that active nitrogen species such as nitrogen radicals and nitrogen ions generated within the plasma combine with the reaction products of other gases forming products that adhere to the sidewall of the PZT layer to prevent the sidewall from etching. The use of nitrogen-containing gas may result in preventing side wall etching due to the generation of nitrogen radicals and nitrogen ions in the plasma.

In one embodiment of the invention, when etching the PZT layer 4, the process gas comprises BCI₃, a carbon-containing gas and a nitrogen-containing gas. The flow rate of the N-containing gas may be substantially the same as the flow rate of the CHF₃ gas.

Fig. 3 shows a plasma etching apparatus employed to etch the Ir layer 5, the Pt layer 3, and the PZT-based ferroelectric layer 4. The substrate 2, after having a multi-layer film formed thereon, is placed in an etching chamber 31 of an etching apparatus 30. The plasma etching apparatus 30 comprises the etching chamber 31 , a gas supply source 32, a high-frequency power source 33, a temperature regulator 34 and a gas exhausting system (not shown). An electrode 35 for supplying high- frequency power, and a substrate support 36 for carrying substrate 2 are disposed in the etching chamber 31. The substrate support 36 has, for example, a heater 36a disposed therein. The heater 36a is controlled by the temperature regulator 34, and the temperature of the substrate support 36 is thereby set to a predetermined temperature. The temperature of the substrate 2 placed on the substrate support 36 is defined by the temperature of the substrate support 36. In the plasma etching apparatus 30, the temperature of the substrate support 36 can be raised to, for example, about 400 degrees, as a temperature within the range suitable for the etching of the PZT-based ferroelectric layer 4. After being placed on the substrate support 36, the substrate 2 is maintained at a temperature exceeding 100 degrees.

Fig. 4 is a circuit diagram showing an example of a memory cell semiconductor 20 device comprising a ferroelectric capacitor 1 and a field effect transistor (FET). The capacitor is formed using an etching process according to embodiments described herein. The capacitor 1 comprises dielectric portions such as the dielectric portions 10 shown in Fig. 1 i. The dielectric portions 10 are ferroelectric and may thereby exhibit hysteresis characteristics, as depicted in Fig. 6, thereby providing the device 20 with a memory effect. In Fig. 6, the abscissa represents an applied electric field and the ordinate represents polarization.

Using the etching process of the present invention, the side-etching of the PZT layer is prevented. Semiconductor devices manufactured using the method of the present invention are advantageous in that the reliability of the devices formed is improved.

The scope of the present invention is not limited to the . embodiments discussed above. For example, while the conductive layers are described above as iridium (Ir) and platinum (Pt) layers, other materials, including other precious metals such as ruthenium (Ru), and the like, as well as conductive oxides such as iridium oxide (Ir0₂) and ruthenium oxide (Ru0₂) may be used. Furthermore, while the ferroelectric layer is described above as a PZT layer, the ferroelectric layer may include other elements such as lanthanum (La), niobium (Nb) and bismuth (Bi). Furthermore, the above description details the use of the etching method for use in the fabrication of a capacitor, the etching method of the present invention may be used to form other devices. Furthermore, while the hard masks are described above as a Siθ2 layer, hard masks comprising a silicon-based inorganic insulating layer or hard masks composed of titanium nitride (TiN) may also be used.

Similarly, the carbon-containing gas is not limited to CHF₃. In general, it may be a compound represented by a chemical formula C_xH_y or C_xH_yF_z, such as, for example, C₂H . Furthermore, the nitrogen-containing gas is not limited to N₂ and may include, for example, NF₃. While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

Claims:

1. A method of etching a ferroelectric layer, the method comprising: - providing a substrate comprising a ferroelectric layer; and supplying a process gas comprising boron trichloride and at least one auxiliary gas selected from the group consisting of a carbon-containing gas and a nitrogen-containing gas.

2. The method of claim 1 wherein the process gas comprises boron trichloride, a carbon-containing gas and a nitrogen-containing gas.

3. The method of claim 2 wherein the carbon-containing gas has a flow rate that is substantially equal to a flow rate of the nitrogen-containing gas.

4. The method of claim 1 , wherein a flow rate of the at least one auxiliary gas is not less than 1 seem and not greater than 10 seem.

5. The method of claim 1 , wherein a flow rate of the at least one auxiliary gas is not less than 1 % by mole and not greater than 10 % by mole with respect to a total flow rate of process gas supplied during etching.

6. The method of claim 1 , wherein the carbon-containing gas is selected from the group consisting of CHF₃ and C₂H₄.

7. The method of claim 1 , wherein the nitrogen-containing gas is selected from the group consisting of N₂ and NF₃.

8. The method of claim 1 , wherein the process gas further comprises argon.

9. The method of claim 1 wherein hard masks are used to etch the ferroelectric layer.

10. The method of claim 1 wherein the ferrorelectric material is lead zirconate titanate (PZT).

11. A method of forming a capacitor, comprising: forming a multi-layer film comprising a first conductive layer, a ferroelectric layer, and a second conductive layer; etching the first conductive layer to form first electrodes; etching the ferroelectric layer with a process gas comprising boron trichloride and an auxiliary gas selected from the group consisting of a carbon-containing gas and a nitrogen-containing gas; and etching the second conductive layer to form the second electrodes.

12. The method of claim 11 , wherein the first conductive layer and the second conductive layer include a material selected from the group consisting of precious metals and conductive oxides.

13. The method of claim 11 , wherein the first conductive layer and the second conductive layer include a material selected from the group consisting of iridium, platinum and ruthenium, iridium oxide (Ir0₂), and ruthenium oxide (Ru0₂).

14. The method of claim 11 wherein the process gas comprises boron trichloride, a carbon-containing gas and a nitrogen-containing gas.

15. The method of claim 11 , wherein the at least one auxiliary gas has a flow rate not less than 1 seem and not greater than 10 seem.

16. The method of claim 11 , wherein the at least one auxiliary gas has a flow rate not less than 1 % by mole and not greater than 10% by mole with respect to a total flow rate of process gas supplied during etching.

17. The method of claim 11 , wherein the carbon-containing gas is selected from the group consisting of CHF3 and C2H4.

18. The method of claim 11 , wherein the nitrogen-containing gas is selected from the group consisting of N₂ and NF₃.

19. The method of claim 11 , wherein the process gas further comprises argon.

20. The method of claim 11 wherein the ferroelectric material is lead zirconate titanate (PZT).

21. The method of claim 11 further comprising: forming hard masks on the second conductive layer; and using the hard masks to etch the second conductive layer, the ferroelectric layer, and the first conductive layer.