# Patent

## Title
Semiconductor manufacturing apparatus for modifying-in-film stress of thin films, and product formed thereby

## Abstract

An apparatus for depositing a thin film on a substrate and product produced thereby are disclosed. In particular, deposition of the thin film is carried out on the substrate having an applied pressure. This applied pressure flexes the substrate to reduce in-plane stresses, wherein removal of the applied pressure after deposition of the thin film modifies the in-film stress for the thin film. With the above-described arrangement, it is possible to minimize the deterioration of electric characteristics of a semiconductor device and the occurrence of defects, such as film delamination, substrate cracks, and the like.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of application Ser. No. 10/391,876, filed Mar. 18, 2003 now U.S. Pat. No. 6,884,718.


FIELD OF THE INVENTION
The present invention relates to methods of controlling in-film stress in thin films of the type used in semiconductor fabrication, and, more particularly, to a method of controlling the state and amount of in-film stress of a barrier material provided on a semiconductor substrate.
BACKGROUND OF THE INVENTION
In many areas of semiconductor processing, it is often necessary to provide consecutive layers of materials that are not stable in contact with each other. For example, aluminum (Al) reacts with silicon at a few hundred ° C. to form “spikes” of an eutectic alloy which can penetrate into the silicon through the source or drain layer causing shorts to the body if a direct Al—Si contact is made. Additionally, silicon (Si) must also be protected during tungsten deposition, as the copious amounts of fluorine present will combine with hydrogen to form hydrofluoric acid (HF), which can attack silicon or silicon dioxide to form “wormholes” under the tungsten layer. Furthermore, copper (Cu) used in IC metallization must not encounter silicon dioxide passivants, as Cu+ ions will diffuse readily through the oxide and contaminate the underlying silicon.
In all the above cases and more, the situation is rescued by employing barrier materials, which are typically metals or nitrides of such metals in most applications that conduct electricity but do not permit interdiffusion and reactions of neighboring materials. However, certain barrier materials exhibit tensile or compressive stress when deposited as a thin film. In some cases, stress will build up because of the processing conditions, thermal expansion, or the mismatch of various characteristics of neighboring materials. As an example, low-Cl and low resistivity TiN films (TiCl4-based) exhibit very high in-film tensile stress when deposited on a silicon substrate.
The conventional method of depositing such thin films includes continuous deposition of a barrier material onto a semiconductor substrate until the desired thickness has been attained. The prior art continuous deposition method results in a structure as seen in prior art FIG. 1: a thin film of the barrier material 10, deposited onto a semiconductor substrate 12. When the thin barrier film made using the prior art process consists of TiN, for example, the thin barrier film 10 after heat treatment exerts a tensile stress 14 on the underlying substrate 12. The force exerted in compressive stress 16 by the substrate 12 is equal and opposite in directionality to the tensile stress 14 of the thin barrier film 10.
If the magnitude of the in-film tensile stress is sufficient, the thin barrier film 10 may crack, buckle, delaminate or pull away from the surface of the substrate 12, or even cause stress-related breakage of metal interconnects limiting applications of the used barrier material. This in-film stress also limits the thickness of such thin barrier films in applications because thicker films have more potential energy to crack and peel. Additionally, high stress levels in such thin barrier films can affect many material properties such as dielectric constant and crystallographic orientation. These damaging effects may occur during the course of the integrated circuit manufacturing process, or at any time throughout the useful lifetime of the integrated circuit device, resulting in yield loss and seriously affecting the reliability of the product seriously.
It would be, therefore, desirable to provide a method of depositing thin barrier films on semiconductor substrates in a manner that addresses in-film stress such that the thin barrier films exhibit reduced tensile or compressive stress following deposition.
SUMMARY OF THE INVENTION
The present invention addresses the above need by providing a method of depositing a thin film of a barrier material on a substrate so that the thin barrier film has a reduced amount of in-film stress. By reducing the amount of stress in the thin barrier film, cracking and delamination of barrier film from the semiconductor device may be addressed.
In one embodiment, provided is a method of modifying in-film stress of a thin barrier film comprising preloading a substrate with a preloaded stress, depositing a barrier material as a thin film on the substrate, and unloading the preloaded stress applied to the substrate.
In another embodiment, a method for fabricating a thin-film structure body is provided. The method comprises flexing a semiconductor substrate, depositing a thin film of a barrier material on the flexed semiconductor substrate, and unflexing the substrate.
In still another embodiment, a method for fabricating a thin-film structure body is provided. The method comprises providing a substrate to a sample holder, flexing the substrate to preload the substrate with tensile stress, depositing a barrier material on the flexed substrate, and unflexing the substrate.
In still another embodiment, a method for fabricating a thin-film structure body is provided. The method comprises providing a substrate to a sample holder, flexing the substrate to preload the substrate with compressive stress, depositing a barrier material on the flexed substrate, and unflexing the substrate.
In yet another embodiment, a method of modifying in-film stress of a thin barrier film is provided. The method comprises providing a substrate to a sample holder, raising a pin to flex the substrate to preload the substrate with a predetermined tensile stress, depositing a barrier material as a thin film on the substrate, and lowering the pin to unload the tensile stress applied to the substrate.
In still yet another embodiment, a method of modifying in-film stress of a thin barrier film is provided. The method comprises providing a substrate to a sample holder, raising a pin to flex the substrate to preload the substrate with a predetermined compressive stress, depositing a barrier material as a thin film on the substrate, and lowering the pin to unload the compressive stress applied to the substrate.
In another embodiment, a method for fabricating a thin-film structure body is provided. The comprises mounting a substrate by clips to a sample holder, situating the sample holder in a deposition chamber, pumping the deposition chamber to a base pressure, gradually heating the substrate to a desired temperature, and raising a pin to flex the substrate to preload the substrate with tensile stress. The method further includes depositing a barrier material on the flexed substrate, and lowering the pin to unflex the substrate.
In another embodiment, a method for fabricating a thin-film structure body is provided. The comprises mounting a substrate by clips to a sample holder, situating the sample holder in a deposition chamber, pumping the deposition chamber to a base pressure, gradually heating the substrate to a desired temperature, and applying a vacuum to flex the substrate to preload the substrate with compressive stress. The method further includes depositing a barrier material on the flexed substrate, and removing the vacuum to unflex the substrate.
In still another embodiment, an apparatus for manufacturing a semiconductor device and for carrying out a process of depositing barrier materials so as to form deposited thin barrier films having a modified in-film stress is provided. The apparatus comprises a chamber in which a semiconductor substrate can be contained, a sample holder adapted to support the semiconductor substrate within the chamber, and a tool for flexing the semiconductor substrate when supported by the sample holder.
In another embodiment provided is a method of forming a DRAM cell. The method comprises providing a substrate having CMOS structures to a sample holder, situating said sample holder in a deposition chamber, flexing the substrate, depositing a thin film of a barrier material on the flexed substrate, and unflexing the substrate.
In another embodiment, provided is a memory device structure comprising a semiconductor substrate having a lightly doped P-type crystal silicon substrate, and having field oxide areas and drain regions and source regions. The memory device structure further includes transistor gate members, including a wordline bounded by insulative material, formed on the surface of the semiconductor substrate, and a barrier film which was disposed over the semiconductor substrate when preloaded with a tensile stress.
In another embodiment, provided is a memory device structure comprising a semiconductor substrate having a lightly doped P-type crystal silicon substrate, and having field oxide areas and drain regions and source regions. The memory device structure further includes transistor gate members, including a wordline bounded by insulative material, formed on the surface of the semiconductor substrate, and a barrier film which was disposed over the semiconductor substrate when preloaded with a compressive stress.
In still another embodiment, provided is a DRAM cell comprising a semiconductor substrate having a lightly doped P-type crystal silicon substrate, and having field oxide areas and drain regions and source regions. The DRAM cell further includes transistor gate members, including a wordline bounded by insulative material, formed on the surface of the semiconductor substrate, and a barrier film which was disposed over the semiconductor substrate, the thick field oxide areas, and the transistor gate members when preloaded with a tensile stress. The barrier film has bitline contacts contacting the source regions for electrical communication with a bitline, and, further, has capacitor contacts contacting the drain regions for electrical communication with capacitors.
In still another embodiment, provided is a DRAM cell comprising a semiconductor substrate having a lightly doped P-type crystal silicon substrate, and having field oxide areas and drain regions and source regions. The DRAM cell further includes transistor gate members, including a wordline bounded by insulative material, formed on the surface of the semiconductor substrate, and a barrier film which was disposed over the semiconductor substrate, the thick field oxide areas, and the transistor gate members when preloaded with a compressive stress. The barrier film has bitline contacts contacting the source regions for electrical communication with a bitline, and, further, has capacitor contacts contacting the drain regions for electrical communication with capacitors.
These and other features and objects of the present invention will be apparent in light of the description of the invention embodied herein.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an enlarged schematic cross-sectional view of a portion of a prior art semiconductive structure,
FIGS. 2-5 illustrate process steps according an embodiment of the present invention, and depict cross-sectional views of a portion of a semiconductor substrate having a thin barrier film deposited thereon;
FIGS. 6-7 illustrate process steps according another embodiment of the present invention, and depict cross-sectional views of a portion of a semiconductor substrate having a thin barrier film deposited thereon; and
FIG. 8 is a schematic cross-sectional side view of a memory array of a DRAM chip formed by a method to reduce in-film stress according to an embodiment of the present invention.



In the drawings, the thicknesses of the various layers of material have been modified for clarity of illustration and are not necessarily true to scale.
DETAILED DESCRIPTION OF THE INVENTION
For purposes of the invention, the term “thick barrier film” will be understood to mean a layer of barrier material, which has a thickness greater than or equal to 5000 Å.
For purposes of the invention, the term “thin barrier film” will be understood to mean a layer of barrier material, which has a thickness less than 5000 Å.
For purposes of the invention, suitable materials for the barrier film are any materials which conduct electricity but do not permit inter-diffusion and reactions of neighboring films, and which possess properties of a low electrical resistivity, high melting point, thermal stability, and good adhesion properties. Such barrier films include, for example, Ti, TiW, TiN, TaN, Ta-based materials, WN, MoN, AlN, CrN, ScN, and any other barrier metal and metal alloy films suitable for the intended application.
For the purposes of this invention, a semiconductor substrate may comprise a silicon wafer, optionally with various components formed therein, including active devices, dielectric layers, barrier layers, underlying metal lines, oxide-filled barrier trenches, and the like.
Referring to FIGS. 2-5, one embodiment of the invention provides a method of modifying in-film (intrinsic) stress for thin barrier films deposited on a surface 20 of a substrate 22, such that thicker barrier films than that found in the prior art may be employed without having the negative effect of increased in-film stress.
As illustrated in FIG. 2, substrate 22 is mounted by clips 24 to a sample holder 26, which is then situated in a deposition chamber 28. It is assumed for the purposes of this discussion that substrate 22 has no intrinsic stress from prior processes, and is generally flat. The deposition chamber 28 is then pumped to a base pressure prior to deposition, such as for example, between about 1 to about 10 Torr. Prior to deposition, substrate 22 is gradually heated to a desired temperature, such as for example, between about 250° C. to about 700° C., and may be cleaned if desired by conventional cleaning processes, such as for example, sputtering.
In FIG. 3, substrate 22 is then warped or flexed into a convex configuration, such as by a retractable pin 30 engaging the undersurface 23 of substrate 22 and being raised in the direction indicated by symbol a. Substrate 22 may be warped or flexed by a number of alternative methods such saddling substrate 22 over pin 30 and lowering clips 24 in the direction indicated by symbol b, by squeezing clips 24 together in the direction indicated by symbol c, or any other means which applies a pressure to deform substrate 22 into a convex configuration to preload tensile stress. The flexing of substrate 22 induces tensile stress, thereby reducing the resulting intrinsic compressive stress realized after depositing a thin barrier film. The range of the preloaded tensile stress is from about 10% to about 200%, and the actual amount of the preloaded tensile stress depends on the intended barrier layer material and desired thickness of the film.
With substrate 22 flexed into a convex configuration illustrated in FIG. 4, a thin barrier film 32 is then provided over surface 20 of substrate 22. The thin barrier film 32 may be provided using any conventional deposition method, such as by reactive ion sputtering, electron beam evaporation, physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer chemical vapor deposition (AL-CVD), and ion-beam assisted deposition (IAD) techniques. The method may also be used to grow a monolayer of the thin barrier film 32 on surface 20. Regardless of the technique used for depositing the thin barrier film 32, it is important the deposited layer(s) adhere securely to one another and/or to substrate 22, as the case may be.
As illustrated by FIG. 5, because of the preloading of tensile stress within substrate 22 prior to deposition and crystallization of the thin barrier film 32, the level of stress in the thin barrier film 32 is reduced, or, in some cases, the state of the stress in the layer is changed. The state and level of stress in the thin barrier film 32 after deposition varies primarily as a function of preloading of tensile stress on substrate 22 and the composition and thickness of the thin barrier film 32. Thus, by appropriate selection of the amount of preloaded tensile stress for substrate 22 and materials for the thin barrier film 32, and by depositing the barrier film to an appropriate thickness, the state and level of stress in the film may be controlled.
In another embodiment, the substrate 22 may be warped or flexed into a concave configuration, such as by raising clips 24 in the direction indicated by symbol d, applying a vacuum to engage the undersurface 23 of substrate 22, such as through retractable pin 30, and lowering pin 30 in the direction indicated by symbol e. Substrate 22 may be warped or flexed by any other means which applies a pressure to deform substrate 22 into a concave configuration to preload a compressive stress. The range of the preloaded compressive stress is from about 10% to about 200%, and the actual amount of the preloaded compressive stress depends on the intended barrier layer material and desired thickness of the film.
Such flexing of substrate 22 induces compressive stress, thereby reducing the resulting intrinsic tensile stress realized after depositing the thin barrier film 32, as illustrated by FIG. 7. Preloading the substrate before deposition of the thin barrier film helps to reduce the amount of in-film stress of barrier material which exhibits very-high in-film compressive stress when deposited on a substrate without a preloaded stress. As before, the thin barrier film 32 may be provided using any conventional deposition method, such as by reactive ion sputtering, electron beam evaporation, physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer chemical vapor deposition (AL-CVD), and ion-beam assisted deposition (IAD) techniques. The method may also be used to grow a monolayer of the thin barrier film 32 on surface 20. Regardless of the technique used for depositing the thin barrier film 32, it is important the deposited layer(s) adhere securely to one another and/or to substrate 22, as the case may be.
Resulting stress after the deposition method of the present invention may be computationally determined. As is known, the mechanical stress is a force in the plane of film 32 acting per unit area of the film cross section. The mechanical stress may be compressive or tensile in character. The total mechanical stress s of a thin barrier film 32 consists of two terms:

s=si+sT  (1)

where si is intrinsic stress, which is a fundamental result of the conditions and method of film growth and is to a large degree a reflection of the film structure and the presence of impurities. Intrinsic stress si is calculated by the expression

si=[Es/6(1−ns)](ds2/df)(1/Rs−1/Rf)  (2)

where Es and ns are respectively the Young's modulus and Poisson ratio of the substrate, ds and df are respectively the substrate and the film thickness, and Rs and Rf are, respectively, the radii of curvature of the substrate without and with the barrier film. The thin barrier film thickness df can be measured by profilometric measurements of film steps obtained using appropriate film masks on each sample.

The thermal stress sT in the barrier film is calculated by the expression:

sT=[Ef/(1−nf)](af−as)(Td−TM)  (3)

where Ef and nf are respectively the Young's modulus and Poisson ratio for the film, af and as are average thermal coefficients of the film and the substrate, and Td and TM are the film deposition temperature and the temperature during the stress measurements, respectively. Accordingly, the amount of flexing of the substrate before deposition of the barrier material can be derived from the above equations in order to give a desired in-film stress level (tensile or compressive).

Alternatively, the in-film stress of film barrier film 32 may be determined based on empirical testing. Such testing involves depositing the barrier film 32 at a range of different thicknesses and substrate flexing, and then measuring the in-film stress levels of the barrier film 32 using, for instance, known reflectivity-measuring techniques. By correlating the characteristics of layers 22 and 32 with the type (i.e., convex or concave) and extent of deformation after deposition of the barrier film, the deposition parameters, i.e., barrier film thickness and amount of substrate flexing, required to achieve a thin barrier film 32 that impart the desired in-film stress (tensile or compressive) in substrate 22 may be determined.
The above-described method of controlling the state and level of in-film stress of thin barrier films deposited on a substrate may be used in the current generation DRAMs. Thus, when used in a DRAM, such as illustrated in FIG. 8, the thin barrier film is deposited in accordance with the deposition techniques discussed above. The stress in such DRAMs may be precisely controlled, as also discussed above. By controlling such in-film stress, the formation of dislocations in the substrate adjacent the barrier layer may be reduced significantly. Because such dislocations apparently provide pathways through which ions may diffuse and charge may leak, by reducing the formation of dislocations, it is believed that the reliability and retention time of the associated DRAM will increase.
For example, a CMOS structure 200 is illustrated in FIG. 6 as a portion of a memory array in a DRAM chip. The CMOS structure 200 comprises a semiconductor substrate 202, such as a lightly doped P-type crystal silicon substrate, which has been oxidized to form thick field oxide areas 204 and exposed to implantation processes to form drain regions 206 and source regions 208. Transistor gate members 212, including a wordline 214 bounded by insulative material 216, are formed on the surface of the semiconductor substrate 202. A barrier film 218 is disposed over the semiconductor substrate 202, the thick field oxide areas 204, and the transistor gate members 212 according to the present invention described above. The barrier film 218 has bitline contacts 222 contacting the source regions 208 for electrical communication with a bitline 224, and, further, has capacitor contacts 226 contacting the drain regions 206 for electrical communication with capacitors 228.
Having described the present invention in detail and by reference to the embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention in the following claims.

## Claims

1. A substrate bearing a thin film of a material having a modified in-film stress, said substrate having a predetermined stress wherein said predetermined stress provides a mechanical stress s to said thin film, said mechanical stress being derived using the following equations:


s=si+sT  (1)

where si is intrinsic stress calculated by the expression:


si=[Es/6(1−ns)](ds2/df)(1/Rs−1/Rf)  (2)


where Es and ns are Young's modulus and Poisson ratio of said substrate, respectively, ds and df are thickness of said substrate and said thin film, respectively, and Rs and Rf are radii of curvature of said substrate without and with said thin film, respectively, and where sT is thermal stress in said thin film calculated by the expression:


sT[Ef/(1−nf)](af−as)(Td−TM)  (3)


where Ef and nf are Young's modulus and Poisson ratio for said thin film, respectively, af and as are average thermal coefficients of said thin film and said substrate, and Td and TM are film deposition temperature and temperature during stress measurement, respectively.

2. The substrate as recited by claim 1, wherein said material is a barrier material.

3. The substrate as recited by claim 1, wherein said material is a barrier material selected from the group consisting of Ti, TiW, TiN, TaN, Ta-based materials, WN, MoN, AlN, CrN, ScN, barrier metals, barrier metal alloys, and combinations thereof.

4. The substrate as recited by claim 1, wherein said thin film is a monolayer of said material on said substrate.

5. The substrate as recited by claim 1, wherein said substrate is a silicon substrate.

6. The substrate as recited by claim 1, wherein said substrate is a doped silicon substrate, wherein said thin film was disposed over the substrate when preloaded with a tensile stress.

7. A semiconductive device comprising the substrate of claim 1, wherein said substrate is a silicon substrate.

8. A semiconductive device comprising the substrate of claim 1, wherein said material is a barrier material.

9. A semiconductive device comprising the substrate of claim 1, wherein said material is a barrier material selected from the group consisting of Ti, TiW, TiN, TaN, Ta-based materials, WN, MoN, AlN, CrN, ScN, barrier metals, barrier metal alloys, and combinations thereof.

10. A semiconductive device comprising the substrate of claim 1, wherein said thin film is a monolayer of said material on said substrate.

11. A semiconductive device comprising the substrate of claim 1, wherein said substrate is a silicon substrate, and said material is a barrier material.

12. A memory device comprising the substrate of claim 1.

13. A memory device comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate.

14. A memory device comprising the substrate of claim 1, wherein said material is a barrier material.

15. A memory device comprising the substrate of claim 1, wherein said material is a barrier material selected from the group consisting of Ti, TiW, TiN, TaN, Ta-based materials, WN, MoN, AlN, CrN, ScN, barrier metals, barrier metal alloys, and combinations thereof.

16. A memory device comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate, and said material is a barrier film.

17. A memory device comprising the substrate of claim 1, wherein said thin film is a monolayer of said material on said substrate.

18. A memory device comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate, wherein said thin film was disposed over the substrate when preloaded with a tensile stress.

19. A memory device comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate having field oxide areas and drain regions and source regions, and said material is a barrier film, said memory device further comprising transistor gate members, including a wordline bounded by insulative material, formed on a surface of the substrate.

20. A DRAM cell, comprising the substrate of claim 1.

21. A DRAM cell comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate having field oxide areas, drain regions, and source regions.

22. A DRAM cell comprising the substrate of claim 1, and transistor gate members formed on a surface of the substrate.

23. A DRAM cell comprising the substrate of claim 1, transistor gate members formed on a surface of the substrate, and a wordline bounded by insulative material.

24. A DRAM cell comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate having oxide areas, said DRAM cell further comprising transistor gate members formed on a surface of the substrate, wherein said thin film was disposed over the substrate, the oxide areas, and the transistor gate members when preloaded with a tensile stress.

25. A DRAM cell comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate having field oxide areas, drain regions, and source regions, said DRAM cell further comprising transistor gate members formed on a surface of the substrate, and a wordline bounded by insulative material, wherein said thin film was disposed over the substrate, the oxide areas, and the transistor gate members when preloaded with a tensile stress, said thin film having bitline contacts contacting the source regions for electrical communication with a bitline, and, further, having capacitor contacts contacting the drain regions for electrical communication with capacitors.

26. A DRAM cell comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate.

27. A DRAM cell comprising the substrate of claim 1, wherein said material is a barrier material.

28. A DRAM cell comprising the substrate of claim 1, wherein said material is a barrier material selected from the group consisting of Ti, TiW, TiN, TaN, Ta-based materials, WN, MoN, AlN, CrN, ScN, barrier metals, barrier metal alloys, and combinations thereof.

29. A DRAM cell comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate, and said material is a barrier film.

30. A DRAM cell comprising the substrate of claim 1, wherein said thin film is a monolayer of said material on said substrate.

31. A DRAM cell comprising the substrate of claim 1, wherein said substrate is a doped silicon substrate, wherein said thin film was disposed over the substrate when preloaded with a tensile stress.

32. An apparatus for providing the substrate of claim 1, said apparatus comprising:
a chamber in which the substrate can be contained;
a sample holder adapted to support the substrate within said chamber; and
a tool for flexing the substrate when supported by said sample holder in order to provide said predetermined stress.

33. The apparatus as recited by claim 32, wherein said tool comprises a retractable pin.

34. The apparatus as recited by claim 32, wherein said tool comprises movable clips and a pin.

35. The apparatus as recited by claim 32, wherein said tool comprises movable clips.

36. The apparatus as recited by claim 32, wherein said tool comprises a port in the sample holder to apply a vacuum to a backside of the substrate, and movable clips to raise the perimeter of the substrate.

37. The apparatus as recited by claim 32, wherein said apparatus is adapted to provide said material when the substrate is in said chamber and provided with said predetermined stress by said tool.

38. The apparatus as recited by claim 32, wherein said apparatus is adapted to deposit said material when the substrate is in said chamber and provided with said predetermined stress by said tool, and wherein said material is a barrier material.

39. The apparatus as recited by claim 32, wherein said apparatus is adapted to deposit said material when the substrate is in said chamber and provided with said predetermined stress by said tool, and wherein said material is a barrier material selected from the group consisting of Ti, TiW, TiN, TaN, Ta-based materials, WN, MoN, AlN, CrN, ScN, barrier metals, barrier metal alloys, and combinations thereof.

40. The apparatus as recited by claim 32, wherein said apparatus is adapted to provide said material to the substrate when the substrate is in said chamber and provided with said predetermined stress by said tool, and wherein said thin film is a monolayer of said material on the substrate.