Methods of growing heteroepitaxial single crystal or large grained semiconductor films and devices thereon

Abstract

A method is disclosed for making semiconductor films from a eutectic alloy comprising a metal and a semiconductor. Through heterogeneous nucleation said film is deposited at a deposition temperature on relatively inexpensive buffered substrates, such as glass. Specifically said film is vapor deposited at a fixed temperature in said deposition temperature where said deposition temperature is above a eutectic temperature of said eutectic alloy and below a temperature at which the substrate softens. Such films could have widespread application in photovoltaic and display technologies.

Claims

1. An electromagnetic device comprising: a substrate, a thin metal film on said substrate, said thin film being between 2-10 nm thick; and a semiconductor film deposited on said substrate, said semiconductor film being deposited from a eutectic alloy at a constant temperature, said constant temperature being above a eutectic temperature of said eutectic alloy, wherein said constant temperature is within a semiconductor growth temperature, said semiconductor growth temperature permitting growth of defect-free semiconductor film.

2. The device of claim 1, wherein the substrate is one of a group consisting of metal tapes, glass, and ceramic.

3. The device of claim 1, wherein said substrate has a buffer layer.

4. The device of claim 3, wherein said buffer layer is comprised of a nitride, Al.sub.2O.sub.3 or MgO.

5. The device of claim 4, wherein said nitride is Titanium Nitride.

6. The device of claim 1 wherein, said semiconductor-growth temperature is above 550 degrees Centigrade.

7. The device of claim 1 wherein, said semiconductor-growth temperature is above 450 degrees Centigrade.

8. The device of claim 1 wherein the eutectic alloy comprises a semiconductor and a metal.

9. The device of claim 8 wherein, said semiconductor is one of a group consisting of germanium, gallium arsenide, gallium nitride and cadmium selenide.

10. The device of claim 8 wherein, said metal is one of a group consisting of gold, aluminum, nickel and silver.

11. The device of claim 8 wherein, said metal is one of a group of-indium and tin.

12. The device of claim 1 wherein said substrate is organic.

13. The device of claim 1 wherein said semiconductor film is a heteroepitaxial film.

14. The device of claim a 1 wherein said substrate is a single crystal.

15. The device of claim 1 wherein said substrate is sapphire.

16. The device of claim 1 wherein said semiconductor film is a single crystal.

17. The device of claim 1 wherein said semiconductor film is textured.

18. The device of claim 1, wherein the semiconductor film is p type.

19. The device of claim 1, wherein the semiconductor film is n type.

20. The device of claim 1, wherein the semiconductor film is used as the surface on which a thicker film is deposited epitaxially.

21. The device of claim 20, wherein said thicker film is an n-type.

22. The device of claim 1, wherein said semiconductor film is deposited by vapor phase, liquid phase, and solid phase.

23. The device of claim 1, wherein said substrate is a heated substrate.

24. The device of claim 1, wherein said semiconductor film is deposited at a temperature greater than 750° C.

25. The device of claim 1, wherein said device has a Schottky barrier.

26. The device of claim 1 wherein the semiconductor film is composed from a material of one of a group consisting of Class IV, Class III-V and Class II-VI elements.

27. The device of claim 26 wherein the material is gallium arsenide.

28. The electromagnetic device of claim 1 wherein once the desired thickness of said semiconductor film is obtained, the substrate with said semiconductor film is cooled to room temperature.

29. An electromagnetic device comprising: a substrate; a thin metal film on said substrate, said thin metal film being between 2-10 nm thick; and a semiconductor film deposited onto said thin metal film, said semiconductor film being deposited on said thin metal film at a deposition temperature, said deposition temperature being a constant temperature, said semiconductor and said thin metal film forming a eutectic liquid; at said constant temperature, increasing concentration of said semiconductor such that the eutectic liquid becomes saturated with said semiconductor and said semiconductor nucleates from said eutectic liquid to form an epitaxial semiconductor film on the substrate.

30. The device of claim 29 wherein the metal is removed by etching.

31. The device of claim 29 wherein said constant temperature is between a eutectic temperature of said eutectic liquid and below a softening temperature of said substrate.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows the phase diagram of the eutectic system Au—Si, taken from the literature (Massalski et al). The melting points of the two elements Au and Si, as well as the eutectic temperature are shown in the figure. The eutectic composition is also indicated. The liquidus line, which defines the boundary between the liquid gold-silicon alloy and solid silicon and a gold-silicon liquid alloy, and on the silicon rich side of the phase diagram, is marked. The figure also shows the change in phases as the composition is changed by depositing silicon on a film of gold held at constant temperature. As the silicon is evaporated on to the gold film, the film comprises of gold solid and a liquid gold-silicon alloy which changes from the point marked by 11 towards 12. Further deposition of silicon results in the film entering the liquid phase region between the points marked 12 and 13. As the silicon deposition continues beyond the point 13, the liquidus boundary, solid silicon nucleates from the liquid which is in equilibrium with a silicon-gold liquid alloy. The solid silicon is deposited on a MgO substrate, forming a highly textured and relatively large grained heterogeneously nucleated film. The thickness of the solid silicon film increases till the deposition is stopped. As it cools Si continues to deposit from the melt while the Au—Si liquid solution becomes richer in gold. This process continues till the eutectic temperature is reached, at which point the liquid solidifies and phase separates into gold and silicon solids.

(2) We have used the phase diagram of the Au—Si eutectic. The Al—Si eutectic is very similar. Here we can heterogeneously nucleate silicon from the Al—Si melt on a single crystal sapphire substrate to form a single crystal heteroepitaxial silicon film.

DETAILED DESCRIPTION OF THE INVENTION

(3) As described above, we have disclosed a method to produce low cost single crystal or large grained epitaxially aligned good quality semiconductor films, in particular silicon, for photovoltaic technology. We have also suggested the use of tapes or glass slabs as substrate materials. The tapes provide strong texture on which buffer layers suitable for silicon growth are present. Our method can produce silicon epitaxy at substantially lower temperatures than those commonly practiced, hence not only minimizing interaction with the surface of the substrate but also enabling the use of glass substrates.

(4) We shall be using the eutectics of silicon with gold and aluminum in describing the details of the invention. It is, however, understood that one skilled in the art can extend the methodology to other semiconductors such as germanium, gallium arsenide, or the cadmium selenide class of photovoltaic materials.

(5) FIG. 1 shows the phase diagram of the eutectic system Au—Si. The eutectic composition is nominally 18.6 atomic percent pct Si and the rest being gold. A thin gold film is first deposited on the buffered substrate. This is followed by silicon deposition. As the silicon concentration increases the film first forms a two phase mixture of gold and liquid gold-silicon. The composition of the latter is determined by the choice of the deposition temperature. With further increase of silicon, the liquid phase region, marked 12, is reached and the remaining gold is dissolved. With still further increase of the amount of silicon, the second liquidus phase boundary, marked 13, is reached and subsequent deposition of silicon atoms results in a solid phase of silicon in equilibrium with the silicon-gold liquid. If the substrate surface is suitably chosen, for example MgO crystals, the solid silicon nucleates heterogeneously onto the surface. The choice of the temperature of deposition is determined by balancing two considerations: quality in terms of defects of the epitaxial film; too low a temperature or too rapid a growth rate of the film at that temperature can introduce defects versus too high a temperature when chemical interaction or mechanical integrity of the substrate limit the usefulness of the material.

(6) We have started with vapor deposition of the metallic film and added silicon to it to traverse the phase diagram from point marked 11 in the figure. However, the metallic element and silicon can be co evaporated to reach any concentration between the points marked 12 and 13 in the figure and subsequently silicon added to reach the desired thickness, before cooling to room temperature.

(7) When the desired thickness of the silicon film is obtained, the substrate with the film is cooled to room temperature. Even though the amount of gold required to catalyze a silicon film is small, it can be further reduced by etching the gold away, for example, by using iodine etch, available commercially. This gold can be recycled

EXAMPLES OF THE INVENTION

(8) The following non-limiting examples are used as illustrations of the various aspects and features of this invention.

Example 1

(9) A good high vacuum system with two electron beam guns, is used to deposit gold and silicon independently. A glass substrate coated with ion beam assisted deposited MgO film is held at temperatures between 575 and 600° C. These are nominal temperatures. It is understood to one skilled in the art that lower or higher temperatures can also be used depending upon the softening temperature of the glass substrate or the reaction kinetics of either gold or silicon with the metallic tape or its buffer layers when used as substrates. A thin gold film of approximately 10 nm thickness is deposited first. This is followed by a silicon film deposited at a rate of 2 nm per minute on top of the gold film. The ratio of the thickness of the gold and silicon films is chosen such that the final composition ensures that a point, marked 13, in FIG. 1 is reached. This point lies at the boundary between the two phase region of solid Si and a liquid Si—Au mixture. For example, for a 10 nm gold film followed a 100 nm silicon film satisfies this condition. Additional silicon film nucleates heterogeneously on the MgO surface to form the desired thin film. The film can now be cooled to room temperature, where the film now comprises of two phases: gold and a relatively large grained and highly textured film of silicon on MgO.

(10) By relatively large grained it is understood to imply a grain size larger than would have been achieved if a silicon film had been deposited under the same conditions but without Au. In the example discussed above the crystallographic texture is strongly [111]. Instead of an insulating substrate such as MgO, it is possible to choose stable and electrically conducting nitrides, such as TiN.

(11) The gold diffuses to the surface of the silicon film, driven by its lower surface energy relative to the silicon surface. The film is etched in a solution, such as a commercially available iodine based chemical, which removes the gold from the two phases, gold and silicon, leaving behind a silicon film.

(12) This silicon film can now be used as the surface on which a thicker silicon film appropriately doped to form a p-n junction, suitable for applications such as photovoltaics, can be deposited. Alternatively, the thin silicon film can be used for heteroepitaxial deposition of other semiconductors, which might be more efficient convertors of sunlight to electricity.

(13) We have used two electron beam guns as an illustrative example. It is understood to one skilled in the art that other methods such as a single gun with multiple hearths, chemical vapor deposition, thermal heating, or sputtering can also be used.

Example 2

(14) A good high vacuum system with two electron beam guns is used to deposit aluminum and silicon independently. A glass substrate or a Ni based substrate coated with a buffer layer of Al.sub.2O.sub.3 is held at temperatures between 600 and 615 degree ° C. These are nominal temperatures. It is understood to one skilled in the art that lower or higher temperatures can also be used depending upon the softening temperature of the glass substrate or the reaction kinetics of either aluminum or silicon with the metallic tape or its buffer layers when used a substrates. The eutectic Al—Si is used instead of the Au—Si example above. A thin Al film 6 nm thick is deposited on the Al.sub.2O.sub.3 followed by a 100 nm thick silicon deposition, and as described in example 1, above, the two phase region comprising of solid silicon and a liquid Si—Al mixture is reached. The deposition is stopped and the sample is slowly cooled to room temperature. Aluminum diffuses through the silicon film, driven by its lower surface energy relative to silicon. The silicon film is heteroepitaxially aligned by the Al.sub.2O.sub.3 surface. The aluminum film on the surface can be etched chemically by well known processes to leave behind a silicon film. The surface of this film can now be used for further growth of epitaxial films either for photovoltaic devices or for field effect transistors.

(15) We note, as stated earlier, that silicon can be grown epitaxially on sapphire but at temperatures higher than 750° C. This is a well established commercial process. However, in the absence of aluminum, silicon deposition at, say, 600° C. produces a fine grained film rather than a heteroepitaxial film, as described above.

Example 3

(16) We describe in this example how different methods of deposition can be combined to take advantage of highly textured films as described in example 1, above. The Si film produced from the deposition of example 1 is etched to remove the Au and then placed back into the vacuum chamber and p.sup.+-Si is deposited on this film. This latter layer serves two purposes: it provides a conducting layer for a photovoltaic device to be subsequently built on it and can be the starting point for a variety of differently configured photovoltaic devices as, for example, a nanowire photovoltaic device. Here a 2-3 nm thick gold film is deposited on the silicon using an electron gun. This 2-3 nm thick gold film breaks up into nanoparticles and is the starting point used by a number of investigators to use chemical vapor deposition to grow nanowires and use these nanowires for photovoltaic devices. The difference is that we show how an inexpensive buffered glass can be used rather than a relatively expensive single crystal Si substrate.

(17) A second possibility is to deposit a Au film of thickness 5 nm as islands on a MgO buffered glass substrate, using lithographic or other means known in the art. A heavily doped silicon (p.sup.+or n.sup.−) film is now deposited on the surface followed by a p- or n-type silicon using electron beam deposition, as described in example 1. The thickness of the heavily doped film is in the micron range whereas the lightly doped film is of the order of 100 nm. The deposition process is now changed and chemical vapor deposition is used for subsequent deposition of suitably doped films of silicon, practiced in the art to grow silicon nanowire photovoltaic devices. The heavier doped silicon film serves the purpose of a conducting layer. Using gold islands has the advantage of controlling the nanowires diameter and length in order to maximize the efficiency of the photovoltaic cell (Kayes et al). Instead of using the insulating MgO buffer layer, a conducting material such as TiN can be used.

Example 4

(18) We describe how different methods of deposition and temperature can be combined to take advantage of films grown as described in Examples 1 and 2, above to produce desirable device structures. Instead of depositing the Al and Si films described in Example 2 above, by two electron beam heated sources in a vacuum, we deposit the Si by decomposition of silane using a chemical vapor deposition chamber. This is a well known industrial process. As in Example 2, we deposit a 6 nm thin film of Al on to a sapphire substrate held at 600° C. We then introduce silane gas into the chamber. At these temperatures, the silane decomposes to form a Si film which reacts with the Al to produce a eutectic solution and when this solution is saturated with Si (the equivalent of point marked 13 in FIG. 1 for an Au—Si alloy) the Si precipitates to heterogeneously nucleate to form an epitaxial film on the surface of the sapphire substrate. This film is continuous and can be doped by adding borane or phosphene gases to silane to obtain p or n type semiconductor behavior. This film can now be used as a basis to construct thin film photovoltaic cells or, alternatively, grow nanowires of Si on top of it by simply lowering the temperature of the substrate below the eutectic temperature of Al—Si (577° C.). For example, if the temperature of deposition is 500° C., Si nanowires will grow on top of the Si film. The Al particles that precipitate out of the Al—Si solution once the temperature of the substrates is below the eutectic temperature now catalytically reduce the silane gas to form nanowires, as described in the literature. These nanowires can be used to build electronic devices, including photovoltaic cells.

(19) While the principles of the invention have been described in connection with specific embodiments, it should be understood clearly that the descriptions, along with the examples, are made by way of example and are not intended to limit the scope of this invention in any manner. For example, a variety of suitable substrates different from the examples given above can be utilized or a different variety of deposition methods and conditions can be employed as would be understood from this invention by one skilled in the art upon reading this document.