US20150187572A1 - Interlayer design for epitaxial growth of semiconductor layers - Google Patents

Interlayer design for epitaxial growth of semiconductor layers Download PDF

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US20150187572A1
US20150187572A1 US14/658,972 US201514658972A US2015187572A1 US 20150187572 A1 US20150187572 A1 US 20150187572A1 US 201514658972 A US201514658972 A US 201514658972A US 2015187572 A1 US2015187572 A1 US 2015187572A1
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oxide
layer
underlayer
metallic
varies
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Erol Girt
Mariana Rodica Munteanu
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Zetta Research and Development LLC AQT Series
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Zetta Research and Development LLC AQT Series
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    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

An interlayer structure that, in one implementation, includes a combination of an amorphous or nano-crystalline seed-layer, and one or more metallic layers, deposited on the seed layer, with the fcc, hcp or bcc crystal structure is used to epitaxially orient a semiconductor layer on top of non-single-crystal substrates. In some implementations, this interlayer structure is used to establish epitaxial growth of multiple semiconductor layers, combinations of semiconductor and oxide layers, combinations of semiconductor and metal layers and combination of semiconductor, oxide and metal layers. This interlayer structure can also be used for epitaxial growth of p-type and n-type semiconductors in photovoltaic cells.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • The present application claims priority to U.S. Provisional Application Ser. No. 61/037,571 filed Mar. 18, 2008, the entirety of which is incorporated by reference herein.
  • TECHNICAL FIELD
  • The present disclosure generally relates to semiconductors and to epitaxial growth of semiconductor layers.
  • BACKGROUND
  • The term epitaxy in general describes an ordered crystalline growth of deposited layers. Epitaxial growth of a semiconductor layer has traditionally been achieved by growing a semiconductor material on top of a single crystal substrate, where the crystal lattice of the single crystal substrate matches the crystal lattice of the deposited semiconductor material. Epitaxial layers may be grown with vapor-phase epitaxy (VPE), a modification of chemical vapor deposition (CVD), liquid-phase epitaxy (LPE), and physical vapor deposition (PVD) (evaporative deposition, electron beam physical vapor deposition, sputter deposition, pulse laser deposition, chatodic-arc deposition, and ion beam physical vapor deposition). If a layer is deposited on a substrate of the same composition, the process is called homoepitaxy; otherwise it is called heteroepitaxy. Epitaxy is used in silicon-based manufacturing processes for bipolar junction transistors (BJTs) and modern complementary metal-oxide-semiconductor (CMOS). Epitaxy is also used in production of laser emitting diodes (LEDs) and in solar cells.
  • SUMMARY
  • The present invention involves the epitaxial growth of semiconductor layers on a substrate alternative to single crystal substrates that involves the use of a metallic interlayer having a closed-packed crystal structure. The following disclosure demonstrates how an epitaxial semiconductor layer can be grown on a glass, metal or plastic substrate. The disclosed invention and embodiments can be used to obviate the need for expensive single crystal substrates traditionally used to epitaxially grow semiconductor layers. In a particular implementation, this is achieved by deposition of an interlayer, which includes an amorphous or nano-crystalline seed-layer and one or more metallic layers with a close-packed crystal structure (e.g., face center cubic (fcc), hexagonal close-packed (hcp) or body center cubic (bcc)), on a substrate prior to sputtering a semiconductor layer. In a particular implementation, the metallic layers with a close-packed crystal structure are polycrystalline with the majority of crystals growing preferentially along a single crystal growth direction. This induces an ordered crystalline growth of grains in semiconductor layers on top of the interlayer structure. In one implementation, these epitaxially grown semiconductor layers can be used in solar cells. For example, this interlayer structure can also be used for epitaxial growth of p-type and n-type semiconductors in photovoltaic cells.
  • DESCRIPTION OF THE DRAWINGS
  • FIGS. 1 a and 1 b illustrate examples of random and epitaxial (respectively) crystal growth direction of grains in a deposited layer perpendicular to the substrate surface.
  • FIG. 2 illustrates example measurement geometries for X-ray structural characterization of deposited layers.
  • FIGS. 3 a, 3 b, 4 a, 4 b, 5 a, and 5 b are plots illustrating the results of 8-20 and rocking curve scans of epitaxially grown semiconductor layers.
  • FIGS. 6 to 13 set forth various example layer structures that can be used to promote epitaxial growth of a semiconductor layer.
  • FIGS. 14 a to 14 l illustrate example layer structures with crystal growth directions.
  • FIG. 15 illustrates example layer structures with epitaxially-grown semiconductor layers that can be used in solar sells.
  • FIGS. 16 a and 16 b illustrate example photovoltaic cell structures according to various implementations of the invention
  • DESCRIPTION OF EXAMPLE EMBODIMENT(S)
  • Introduction—Layer Growth And Characterization
  • If a deposited layer consists of grains with crystalline structure, each grain can grow along a different growth direction. The growth direction is defined as the crystal growth direction of grains in a deposited layer perpendicular to the substrate surface. For example, consider a layer that consists of grains with fcc crystal structure. These grains can grow along a single growth direction (for example [111], as shown in FIG. 1 b) or along different growth directions (as shown in FIG. 1 a). If the grains grow along a single growth direction, the growth is epitaxial and the layer is called an epitaxially-grown layer. Otherwise, if grains grow along different growth directions (see FIG. 1 a, where [111] crystal direction of grains is oriented along different directions) the growth is random.
  • Crystal growth directions [111], [-111], [1-11], [11-1], [-1-11], [1-1-1], [-11-1], and [-1-1-1] are equivalent and collectively are referred to as <111> directions. In the following text, the notation <111> refers to all equivalent [111] directions, <0001> for all equivalent [0001] directions, and <110> for all equivalent [110] directions.
  • The structural characterization of deposited layers may be carried out by X-ray diffraction (XRD) using θ-2θ and rocking curve scans. Measurement geometry is described in FIG. 2. In a θ-2θ scan, the angle between an incident X-ray beam and the substrate surface, θ1, is the same as the angle between the reflected X-ray beam and the substrate surface, θ2, (θ1=θ2=θ). In the rocking curve scan, the angle between the incident and reflected beams, θ3, is kept constant (i.e., θ1+θ2 is kept constant) and the sample is rocked by angle ω, so that the angle between the incident X-ray beam and the substrate, θ1, varies(180-θ3)/2-ω/2 to (180-θ3)/2+ω/2. In both measurements, the imaginary plane formed by incident and diffracted X-ray beams, see FIG. 2, is perpendicular to the substrate surface. The θ-2θ scan can be used to detect the growth direction of grains in the deposited layer—i.e., crystal growth direction of grains in a deposited layer perpendicular to the substrate surface. The rocking curve scan can be used to determine the degree of alignment of the growth directions of grains with the direction normal to the substrate surface in the layer. The measure of alignment between the growth directions of grains in the layer is often expressed as the full width at half maximum (FWHM) of the peak obtained as a result of the rocking curve scan. This peak is narrow for a high degree of alignment between the growth directions of grains in the layer and is wide for a low degree of alignment between the growth directions of grains in the layer. Theory predicts FWHM of a single crystal on the order of 0.0030 for typical experimental conditions. However, most single crystals exhibit FWHM from 0.030 to 0.30.
  • Experimental Results
  • We grew a layer structure that includes: 1) an amorphous seed layer, 2) an fcc underlayer formed over the seed layer, and 3) a semiconductor layer formed over the fcc underlayer, all on top of a glass substrate (glass substrate/seed layer/fcc underlayer/semiconductor layer). After sputtering the fcc underlayer, and before sputtering the semiconductor layer, the glass substrate was heated to 300° C. We also grew a layer structure that includes: 1) an amorphous seed layer, 2) an fcc underlayer formed over the seed layer, 3) a bcc underlayer formed over the fcc underlayer, and 4) a semiconductor layer formed over the bcc underlayer. The substrate was heated to 300° C. after sputtering the fcc underlayer and before sputtering the bcc underlayer. In this particular experiment, argon, Ar, was used as the sputter gas. However, other gases—such as helium (He), neon (Ne), krypton (Kr), xenon (Xe), nitrogen (N2), oxygen (θ2) and/or hydrogen (H)—can also be used.
  • FIG. 3 a to FIG. 5 b show θ-2θ and rocking curve scans obtained from the following layer structures: 1) Seed layer/Au fcc underlayer/Heat/Si semiconductor layer, 2) Seed layer/Ni fcc underlayer/Heat/Si semiconductor layer and 3) Seed layer/Au fcc underlayer/Heat/Mo bcc underlayer/Si semiconductor layer. In structure 1) Seed layer/Au/Heat/Si and structure 3) Seed layer/Au/Heat/Mo/Si, the grains of the Si layer grows along <111> growth directions. The term “Heat” in the structures described above refers to the heating of the substrate to a desired temperature (e.g., 300 C) prior to depositing a succeeding layer. The presence of the Mo layer between Au and Si in structure 3) [Seed layer/Au/Heat/Mo/Si] improves growth of Si grains along <111> crystal directions. This was deduced from rocking curve scans presented in FIG. 1 b, and FIG. 3 b that show that FWHM of <111> directions is reduced from 1.1° in structure 1) Seed layer/Au/Heat/Si, to 0.23° in structure 3) Seed layer/Au/Heat/Mo/Si. In the structure 3) [Seed layer/Au/Heat/Mo/Si], the growth directions of the Si layer is as good as in some single crystal structures. This shows that this seed layer/underlayer structure can be used to achieve highly directional epitaxial growth of the Si layer. Previously, highly directional epitaxial growth has been achieved only by growing Si on top of a single crystal substrate. In structure 2) [Seed layer/Ni/Heat/Si], Si grows along <220> growth directions. The Si layer is also highly oriented; FWHM of Si <220> is 3.95°.
  • In the investigated structures 1) Seed layer/Au/Heat/Si, 2) Seed layer/Ni/Heat/Si and 3) Seed layer/Au/Heat/Mo/Si, both Au and Ni grow preferentially along <111> growth directions, while Mo grows preferentially along the <110> direction. FIG. 3 a shows that majority of Au grains grow along <111> direction but some of Au grains also grow along <200>, <220> and <311> directions. In the structure 3) Seed layer/Au/Heat/Mo/Si the Mo layer is thin, so <110> Mo growth direction cannot be detected from FIG. 5 a. Both Ni and Au have fcc crystal structures; however, Au has a larger lattice constant, a, than Ni (a(Ni)=0.3524 nm and a(Au)=0.4079 rim). Thus, the size of the lattice constant may be important in determining the growth direction of Si layer.
  • Heat may also be an important sputter parameter for Si layer growth. If we grow 1) Seed layer/Au/Si, and 2) Seed layer/Ni/Si layer structures at room temperature, 0-20 scans do not show any Si diffraction peaks. This indicates that Si has an amorphous or nanocrystalline structure. Also, the presence of heat may be necessary for obtaining epitaxial growth of some semiconductor layers. As described above, the substrate may be heated to at least 200° C. (e.g. 300° C.), for example, prior to sputtering an Si semiconductor layer. Heating can be also used to increase the grain size of underlayers and semiconductors that may be desired in some applications.
  • Example Structures for Promoting Epitaxial Growth
  • The following describes various layer structures that can be used to promote epitaxial growth of a semiconductor layer. FIG. 6 to FIG. 13 illustrate structures that may be used to set epitaxial growth of a semiconductor on top of a non-single-crystal substrate:
  • 1) Underlayer1/semiconductor layers (FIG. 6);
  • 2) Underlayer1/Underlayer2/semiconductor layers (FIG. 7);
  • 3) Underlayer1/Underlayer2/Underlayer3/semiconductor layers (FIG. 8);
  • 4) Underlayer1/Underlayer2/Underlayer3/Underlayer4/semiconductor layers (FIG. 9);
  • 5) Seed layer/Underlayer1/semiconductor layers (FIG. 10);
  • 6) Seed layer/Underlayer1/Underlayer2/semiconductor layers (FIG. 11);
  • 7) Seed layer/Underlayer1/Underlayer2/Underlayer3/semiconductor layers (FIGS. 12); and
  • 8) Seed layer/Underlayer1/Underlayer2/Underlayer3/Underlayer4/semiconductor layers (FIG. 13).
  • Underlayerl consists of at least one fcc, hcp or bcc layer. For example, Underlayerl may include one o