WO2002029872A1 - Semiconductor structure including a partially annealed layer - Google Patents
Semiconductor structure including a partially annealed layer Download PDFInfo
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- WO2002029872A1 WO2002029872A1 PCT/US2001/027711 US0127711W WO0229872A1 WO 2002029872 A1 WO2002029872 A1 WO 2002029872A1 US 0127711 W US0127711 W US 0127711W WO 0229872 A1 WO0229872 A1 WO 0229872A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02488—Insulating materials
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/02505—Layer structure consisting of more than two layers
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/0251—Graded layers
Definitions
- This invention relates generally to semiconductor structures and devices and to a method for their fabrication, and more specifically to semiconductor structures including a partially annealed layer, devices formed using these structures, and to the fabrication and use of the structures and devices.
- GaAs Gallium arsenide
- silicon wafers are available up to about 300 mm and are widely available at 200 mm.
- the 150 mm GaAs wafers are many times more expensive than are their silicon counterparts. Wafers of other compound semiconductor materials are even less available and are more expensive than
- a thin film of high quality monocrystalline compound semiconductor material was available at low cost, a variety of semiconductor devices could advantageously be fabricated in that film at a low cost compared to the cost of fabricating such devices on a bulk wafer of compound semiconductor material or in an epitaxial film of such material on a bulk wafer of compound semiconductor material.
- a thin film of high quality monocrystalline compound semiconductor material could be realized on a bulk wafer such as a silicon wafer, an integrated device structure could be achieved that took advantage of the best properties of both the silicon and the compound semiconductor material.
- FIGS. 1, 2, 3, 9, 10 illustrate schematically, in cross section, device structures in accordance with various embodiments of the invention
- FIG. 4 illustrates graphically the relationship between maximum attainable film thickness and lattice mismatch between a host crystal and a grown crystalline overlayer
- FIG. 5 illustrates a high resolution Transmission Electron Micrograph of a structure including a monocrystalline accommodating buffer layer
- FIG. 6 illustrates an x-ray diffraction spectrum of a structure including a monocrystalline accommodating buffer layer
- FIG. 7 illustrates a high resolution Transmission Electron Micrograph of a structure including an amorphous oxide layer
- FIG. 8 illustrates an x-ray diffraction spectrum of a structure including an amo ⁇ hous oxide layer.
- FIG. 1 illustrates schematically, in cross section, a portion of a semiconductor structure 20 suitable for growing a monocrystalline film such as a compound semiconductor layer over a substrate.
- Semiconductor structure 20 includes a monocrystalline substrate 22, accommodating buffer layer 24 comprising a monocrystalline material, and an anneal cap layer 30.
- the term "monocrystalline” shall have the meaning commonly used within the semiconductor industry.
- the term shall refer to materials that are a single crystal or that are substantially a single crystal and shall include those materials having a relatively small number of defects such as dislocations and the like as are commonly found in substrates of silicon or germanium or mixtures of silicon and germanium and epitaxial layers of such materials commonly found in the semiconductor industry.
- structure 20 also includes an amorphous intermediate layer 28 positioned between substrate 22 and accommodating buffer layer 24.
- Structure 20 may also include a template layer (not illustrated) between the accommodating buffer layer and a subsequently grown cap layer; alternatively, layer 30 may serve as both a cap and a template for subsequent monocrystalline layer growth above the accommodating buffer layer.
- the template layer helps to initiate the growth of a monocrystalline layer above the accommodating buffer layer.
- the amorphous intermediate layer helps to relieve the strain in the accommodating buffer layer and by doing so, aids in the growth of a high crystalline quality accommodating buffer layer.
- Substrate 22, in accordance with an embodiment of the invention is a monocrystalline semiconductor wafer, preferably of large diameter.
- the wafer can be of a material from Group IN of the periodic table, and preferably a material from Group INA.
- Group IN semiconductor materials include silicon, germanium, mixed silicon and germanium, mixed silicon and carbon, mixed silicon, germanium and carbon, and the like.
- substrate 22 is a wafer containing silicon or germanium, and most preferably is a high quality monocrystalline silicon wafer as used in the semiconductor industry.
- Accommodating buffer layer 24 is preferably a monocrystalline oxide or nitride material epitaxially grown on the underlying substrate.
- amorphous intermediate layer 28 is grown on substrate 22 at the interface between substrate 22 and the growing accommodating buffer layer by the oxidation of substrate 22 during the growth of layer 24.
- the amorphous intermediate layer serves to relieve strain that might otherwise occur in the monocrystalline accommodating buffer layer as a result of differences in the lattice constants of the substrate and the buffer layer.
- lattice constant refers to the distance between atoms of a cell measured in the plane of the surface. If such strain is not relieved by the amorphous intermediate layer, the strain may cause defects in the crystalline structure of the accommodating buffer layer. Defects in the crystalline structure of the accommodating buffer layer, in turn, would make it difficult to achieve a high quality crystalline structure in films subsequently deposited or grown over the accommodating buffer layer.
- Accommodating buffer layer 24 is preferably a monocrystalline oxide or nitride material selected for its crystalline compatibility with the underlying substrate and with the overlying monocrystalline material (e.g., a monocrystalline layer of compound semiconductor material).
- the material could be an oxide or nitride having a lattice structure matched to the substrate and to the subsequently applied semiconductor material.
- Materials that are suitable for the accommodating buffer layer include metal oxides such as the alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal hafnates, alkaline earth metal tantalates, alkaline earth metal ruthenates, alkaline earth metal niobates, alkaline earth metal vanadates, alkaline earth metal tin-based perovskites, lanthanum aluminate, lanthanum scandium oxide, and gadolinium oxide. Additionally, various nitrides such as gallium nitride, aluminum nitride, and boron nitride may also be used for the accommodating buffer layer.
- metal oxides such as the alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal hafnates, alkaline earth metal tantalates, alkaline earth metal ruthenates, alkaline earth metal niobates, alkaline earth metal vanadates, alkaline earth metal tin
- these materials are insulators, although strontium ruthenate, for example, is a conductor.
- these materials are metal oxides or metal nitrides, and more particularly, these metal oxides or nitrides are a perovskite structure, having at least two different metallic elements. In some specific applications, the metal oxides or nitride may include three or more different metallic elements.
- Amorphous interface layer 28 is preferably an oxide formed by the oxidation of the surface of substrate 22, and more preferably is composed of a silicon oxide.
- the thickness of layer 28 is sufficient to relieve strain attributed to mismatches between the lattice constants of substrate 22 and accommodating buffer layer 24.
- layer 28 has a thickness in the range of approximately 0.5-5 nm.
- Anneal cap layer 30 may include any material that prevents undesired degradation of layer 24, or a portion thereof, during an anneal process.
- layer 30 includes a layer of monocrystalline material, such as a monocrystalline semiconductor material.
- a monocrystalline compound semiconductor layer is formed over accommodating buffer layer 24, layer 30 may include a thin layer of the monocrystalline compound semiconductor layer.
- FIG. 2 illustrates, in cross section, a portion of a semiconductor structure 40 in accordance with a further embodiment of the invention. Structure 40 is similar to the previously described semiconductor structure 20, except that an additional monocrystalline compound semiconductor material layer 26 is formed above anneal cap layer 30.
- structure 40 may include an additional buffer layer positioned between template layer 30 and the overlying layer of compound semiconductor material layer.
- the additional buffer layer formed of, for example, a semiconductor or compound semiconductor material, serves to provide a lattice compensation when the lattice constant of the accommodating buffer layer cannot be adequately matched to the overlying monocrystalline material layer.
- the compound semiconductor material of layer 26 (and of the accommodating buffer layer) can be selected, as needed for a particular semiconductor structure, from any of the Group III A and VA elements (III-N semiconductor compounds), mixed III-V compounds, Group II(A or B) and VIA elements (II-NI semiconductor compounds), and mixed II-NI compounds.
- Examples include gallium arsenide (GaAs), gallium indium arsenide (GalnAs), gallium aluminum arsenide (GaAlAs), indium phosphide (InP), cadmium sulfide (CdS), cadmium mercury telluride (CdHgTe), zinc selenide (ZnSe), zinc sulfur selenide (ZnSSe), and the like.
- Suitable template materials chemically bond to the surface of the accommodating buffer layer 24 at selected sites and provide sites for the nucleation of the epitaxial growth of the subsequent compound semiconductor layer 26. Appropriate materials for the template are discussed below.
- FIG. 3 schematically illustrates, in cross section, a portion of a semiconductor structure 34 in accordance with another exemplary embodiment of the invention.
- Structure 34 is similar to structure 40, except that structure 34 includes an amo ⁇ hous buffer material 36 formed of portions of layers 28 and 24.
- amo ⁇ hous material 36 may be formed by first forming an accommodating buffer layer and an amo ⁇ hous interface layer in a similar manner to that described above. Anneal cap 30 is then formed overlying the monocrystalline accommodating buffer layer.
- the accommodating buffer layer is then exposed to a laser anneal process to convert a portion of the monocrystalline accommodating buffer layer to an amo ⁇ hous structure, such that structure 34 includes a first portion 38 that was exposed to the anneal process and a second portion 40 that was not exposed or that was shielded from the anneal process.
- Amo ⁇ hous material 36 formed in this manner comprises materials from both the accommodating buffer and interface layers, which amo ⁇ hous layers may or may not amalgamate. Thus, material 36 may comprise one or two amo ⁇ hous layers. Formation of amo ⁇ hous material 36 provides a true compliant substrate in portion 38 of structure 34 for subsequent processing ⁇ e.g., compound semiconductor layer 26 formation and a monocrystalline oxide material in second portion 40 which may be used to form devices such as wave guides.
- Layer 30 may serve as both an anneal cap during material 36 formation and as a template for subsequent semiconductor layer 26 formation.
- layer 30 is thick enough to provide a suitable template for layer 26 growth (at least one monolayer) and thin enough to allow layer 26 to form as a substantially defect free monocrystalline semiconductor compound.
- monocrystalline substrate 22 is a silicon substrate oriented in the (100) direction.
- the silicon substrate can be, for example, a silicon substrate as is commonly used in making complementary metal oxide semiconductor (CMOS) integrated circuits having a diameter of about 200-300 mm.
- accommodating buffer layer 24 is a monocrystalline layer of Sr z Ba ⁇ -z TiO 3 where z ranges from 0 to 1 and the amo ⁇ hous intermediate layer is a layer of silicon oxide (SiO x ) formed at the interface between the silicon substrate and the accommodating buffer layer.
- the value of z is selected to obtain one or more lattice constants closely matched to corresponding lattice constants of subsequently formed layers (e.g., layer 26).
- the accommodating buffer layer can have a thickness of about 2 to about 100 nanometers (nm) and preferably has a thickness of about 10 nm. In general, it is desired to have an accommodating buffer layer thick enough to isolate the subsequently formed layer(s) from the substrate to obtain the desired electrical and optical properties. Layers thicker than 100 nm usually provide little additional benefit while increasing cost unnecessarily; however, thicker layers may be fabricated if needed.
- the amo ⁇ hous intermediate layer of silicon oxide can have a thickness of about 0.5-5 nm, and preferably a thickness of about 1.5-2.5 nm.
- material layer 26 is a layer of gallium arsenide (GaAs) or aluminum gallium arsenide (AlGaAs) having a thickness of about, l_nm to about 100 micrometers ( ⁇ m) and preferabl a thickness of about 0.5 ⁇ m to 10 ⁇ m. The thickness generally depends on the application for which the layer is being prepared.
- a template layer is formed by capping the oxide layer.
- the template layer is preferably 1-10 monolayers of Ti-As, Sr-O-As, Sr-Ga-O, or Sr-Al-O.
- 1-2 monolayers of Ti-As or Sr- Ga-O have been shown to successfully grow GaAs layers.
- monocrystalline substrate 22 is a silicon substrate as described above.
- the accommodating buffer layer is a monocrystalline oxide of strontium or barium zirconate or hafnate in a cubic or orthorhombic phase with an amo ⁇ hous intermediate layer of silicon oxide formed at the interface between the silicon substrate and the accommodating buffer layer.
- the accommodating buffer layer can have a thickness of about 2-100 nm and preferably has a thickness of at least 5 nm to ensure adequate crystalline and surface quality and is formed of a monocrystalline SrZrO 3 , BaZrO 3 , SrHfO 3 , BaSnO 3 or BaHfO 3 .
- a monocrystalline oxide layer of BaZrO 3 can grow at a temperature of about 700 °C.
- the lattice structure of the resulting crystalline oxide exhibits a 45 degree rotation with respect to the substrate silicon lattice structure.
- the compound semiconductor material of layer 26 can be, for example, indium phosphide (InP), indium gallium arsenide (InGaAs), aluminum indium arsenide, (AlInAs), or aluminum gallium indium arsenic phosphide (AlGalnAsP), having a thickness of about 1.0 nm to 10 ⁇ m.
- a suitable template for this structure is 1-10 monolayers of zirconium-arsenic (Zr-As), zirconium-phosphorus (Zr-P), hafnium- arsenic (Hf-As), hafnium-phosphorus (Hf-P), strontium-oxygen-arsenic (Sr-O-As), strontium-oxygen-phosphorus (Sr-O-P), barium-oxygen-arsenic (Ba-O-As), indium- strontium-oxygen (In-Sr-O), or. barium-oxygen-phosphorus (Ba-O-P), and preferably 1- 2 monolayers of one of these materials.
- the surface is terminated with 1-2 monolayers of zirconium followed by deposition of 1-2 monolayers of arsenic to form a Zr-As template.
- a monocrystalline layer of the compound semiconductor material from the indium phosphide system is then grown on the template layer.
- the resulting lattice structure of the compound semiconductor material exhibits a 45 degree rotation with respect to the accommodating buffer layer lattice structure and a lattice mismatch to (100) InP of less than 2.5%, and preferably less than about 1.0%.
- a structure is provided that is suitable for the growth of an epitaxial film of a II-NI material overlying a silicon substrate.
- the substrate is preferably a silicon wafer as described above.
- a suitable accommodating buffer layer material is Sr x Ba 1-x TiO 3 , where x ranges from 0 to 1, having a thickness of about 2-100 nm and preferably a thickness of about 5-15 nm.
- the II-NI compound semiconductor material can be, for example, zinc selenide (ZnSe) or zinc sulfur selenide (ZnSSe).
- a suitable template for this material system includes 1- 10 monolayers of zinc-oxygen (Zn-O) followed by 1-2 monolayers of an excess of zinc followed by the selenidation of zinc on the surface.
- a template can be, for example, 1-10 monolayers of strontium-sulfur (Sr-S) followed by the ZnSeS .
- This embodiment of the invention is an example of structure 40 illustrated in FIG. 2, including an additional buffer layer (not illustrated) inte ⁇ osed between the accommodating buffer layer and layer 26.
- Substrate 22, monocrystalline oxide layer 24, and monocrystalline compound semiconductor material layer 26 can be similar to those described in example 1.
- the additional buffer layer serves to alleviate any strains that might result from a mismatch of the crystal lattice of the accommodating buffer layer and the lattice of the monocrystalline material of layer 26.
- the buffer layer can be a layer of germanium or a GaAs, an aluminum gallium arsenide (AlGaAs), an indium gallium phosphide (InGaP), an aluminum gallium phosphide (AlGaP), an indium gallium arsenide (InGaAs), an aluminum indium phosphide (AllnP), a gallium arsenide phosphide (GaAsP), or an indium gallium phosphide (InGaP) strain compensated superlattice.
- the buffer layer includes a GaAs x P 1-x superlattice, wherein the value of x ranges from 0 to 1.
- the buffer layer includes an In y Ga 1-y P superlattice, wherein the value of y ranges from 0 to 1.
- the lattice constant is varied from bottom to top across the superlattice to create a match between lattice constants of the underlying oxide and the overlying monocrystalline material.
- the compositions of other materials, such as those listed above, may also be similarly varied to manipulate the lattice constant of the additional buffer layer in a like manner.
- the superlattice can have a thickness of about 50-500 nm and preferably has a thickness of about 100-200 nm.
- the template for this structure can be the same of that described in example 1.
- the buffer layer can be a layer of monocrystalline germanium having a thickness of 1-50 nm and preferably having a thickness of about 2-20 nm.
- a template layer of either germanium-strontium (Ge-Sr) or germanium-titanium (Ge-Ti) having a thickness of about one monolayer can be used as a nucleating site for the subsequent growth of the monocrystalline material layer.
- the formation of the oxide layer is capped with either a monolayer of strontium or a monolayer of titanium to act as a nucleating site for the subsequent deposition of the monocrystalline germanium.
- the monolayer of strontium or titanium provides a nucleating site to which the first monolayer of germanium can bond.
- Substrate material 22, accommodating buffer layer 24, monocrystalline compound semiconductor material layer 26 and template layer 30 can be the same as those described above in example 2.
- an additional buffer layer is inserted between the accommodating buffer layer and an overlying monocrystalline material layer.
- the additional buffer layer a monocrystalline material, can be, for example, a graded layer of indium gallium arsenide (InGaAs) or indium aluminum arsenide (InAlAs).
- the buffer layer includes InGaAs, in which the indium composition varies from 0 to about 47%).
- the additional buffer layer preferably has a thickness of about 10-30 nm.
- Varying the composition of the buffer layer from GaAs to InGaAs serves to provide a lattice match between the underlying monocrystalline oxide material and the overlying layer of monocrystalline compound semiconductor material.
- Such a buffer layer is especially advantageous if there is a lattice mismatch between accommodating buffer layer 24 and monocrystalline material layer 26.
- Substrate material 22, template layer 30, and monocrystalline material layer 26 may be the same as those described above in connection with example 1.
- Amo ⁇ hous material 36 is an amo ⁇ hous oxide layer which is suitably formed of a combination of amo ⁇ hous intermediate layer materials (e.g. , layer 28 materials as described above) and accommodating buffer layer materials (e.g., layer 24 materials as described above).
- amo ⁇ hous material 36 may include a combination of SiO x and SrzBa ⁇ z TiO (where z ranges from 0 to l),which combine or mix, at least partially, during an anneal process to form amo ⁇ hous oxide material 36 in region 38 of structure 34.
- the thickness of layers 24, 28 and 36 may vary from application to application and may depend on such factors as desired insulating properties of the layers, type of material comprising layer 26, and the like. In accordance with one exemplary aspect of the present embodiment, material 36 thickness is about 2 nm to about 100 nm, preferably about 2-10 nm, and more preferably about 5-6 nm.
- substrate 22 is a monocrystalline substrate such as a monocrystalline silicon substrate.
- the crystalline structure of the monocrystalline substrate is characterized by a lattice constant and by a lattice orientation.
- accommodating buffer layer 24 is also a monocrystalline material and the lattice of that monocrystalline material is characterized by a lattice constant and a crystal orientation.
- the lattice constants of the accommodating buffer layer and the monocrystalline substrate must be closely matched or, alternatively, must be such that upon rotation of one crystal orientation with respect to the other crystal orientation, a substantial match in lattice constants is achieved.
- the terms "substantially equal” and “substantially matched” mean that there is sufficient similarity between the lattice constants to permit the growth of a high quality crystalline layer on the underlying layer.
- FIG. 4 illustrates graphically the relationship of the achievable thickness of a grown crystal layer of high crystalline quality as a function of the mismatch between the lattice constants of the host crystal and the grown crystal.
- Curve 42 illustrates the boundary of high crystalline quality material. The area to the right of curve 42 represents layers that have a large number of defects. With no lattice mismatch, it is theoretically possible to grow an infinitely thick, high quality epitaxial layer on the host crystal. As the mismatch in lattice constants increases, the thickness of achievable, high quality crystalline layer decreases rapidly. As a reference point, for example, if the lattice constants between the host crystal and the grown layer are mismatched by more than about 2%, monocrystalline epitaxial layers in excess of about 20 nm cannot be achieved.
- substrate 22 is a (100) or (H I) oriented monocrystalline silicon wafer and accommodating buffer layer 24 is a layer of strontium barium titanate.
- Substantial matching of lattice constants between these two materials is achieved by rotating the crystal orientation of the titanate material by 45° with respect to the crystal orientation of the silicon substrate wafer.
- the inclusion in the structure of amo ⁇ hous interface layer 28, a silicon oxide layer in this example, if it is of sufficient thickness, serves to reduce strain in the titanate monocrystalline layer that might result from any mismatch in the lattice constants of the host silicon wafer and the grown titanate layer.
- a high quality, thick, monocrystalline titanate layer is achievable.
- layer 26 is a layer of epitaxially grown monocrystalline material and that crystalline material is also characterized by a crystal lattice constant and a crystal orientation.
- the lattice constant of layer 26 differs from the lattice constant of substrate 22.
- the accommodating buffer layer must be of high crystalline quality.
- substantial matching between the crystal lattice constant of the host crystal, in this case, the monocrystalline accommodating buffer layer, and the grown crystal is desired.
- this substantial matching of lattice constants is achieved as a result of rotation of the crystal orientation of the grown crystal with respect to the orientation of the host crystal.
- the grown crystal is gallium arsenide, aluminum gallium arsenide, zinc selenide, or zinc sulfur selenide and the accommodating buffer layer is monocrystalline Sr x Ba 1-x TiO 3 , substantial, matching, of .crystal lattice_constants of the two materials is achieved, wherein the crystal orientation of the grown layer is rotated by 45° with respect to the orientation of the host monocrystalline oxide.
- the host material is a strontium or barium zirconate or a strontium or barium hafnate or barium tin oxide and layer 26 is indium phosphide or gallium indium arsenide or aluminum indium arsenide
- substantial matching of crystal lattice constants can be achieved by rotating the orientation of the grown crystal layer by 45° with respect to the host oxide crystal.
- a crystalline buffer layer between the host oxide and the grown layer can be used to reduce strain in the grown monocrystalline layer that might result from small differences in lattice constants. Better crystalline quality in the grown monocrystalline layer can thereby be achieved.
- the following example illustrates a process, in accordance with one embodiment of the invention, for fabricating a semiconductor structure such as the structures depicted in FIGS. 1 - 3.
- the process starts by providing a monocrystalline semiconductor substrate comprising silicon or germanium.
- the semiconductor substrate is a silicon wafer having a (100) orientation.
- the substrate is preferably oriented on axis or, at most, about 0.5° off axis.
- At least a portion of the semiconductor substrate has a bare surface, although other portions of the substrate, as described below, may encompass other structures.
- the term "bare" in this context means that the surface in the portion of the substrate has been cleaned to remove any oxides, contaminants, or other foreign material.
- bare silicon is highly reactive and readily forms a native oxide.
- the term "bare" is intended to encompass such a native oxide.
- a thin silicon oxide may also be intentionally grown on the semiconductor substrate, although such a grown oxide is not essential to the process in accordance with the invention.
- the native oxide layer In order to epitaxially grow a monocrystalline oxide layer overlying the monocrystalline substrate, the native oxide layer must first be removed to expose the crystalline structure of the underlying substrate. The following process is preferably carried out by molecular beam epitaxy (MBE), although other epitaxial processes may also be used in accordance with the present invention.
- MBE molecular beam epitaxy
- the native oxide can be removed by first .thermally depositing a_thin layer of strontium, barium, a combination of strontium and barium, or other alkali earth metals or combinations of alkali earth metals in an MBE apparatus.
- the substrate is then heated to a temperature of about 750° C to cause the strontium to react with the native silicon oxide layer.
- the strontium serves to reduce the silicon oxide to leave a silicon oxide-free surface.
- the resultant surface which exhibits an ordered 2x1 structure, includes strontium, oxygen, and silicon.
- the ordered 2x1 structure forms a template for the ordered growth of an overlying layer of a monocrystalline oxide.
- the template provides the necessary chemical and physical properties to nucleate the crystalline growth of an overlying layer.
- the native silicon oxide can be converted and the substrate surface can be prepared for the growth of a monocrystalline oxide layer by depositing an alkali earth metal oxide, such as strontium oxide, strontium barium oxide, or barium oxide, onto the substrate surface by MBE at a low temperature and by subsequently heating the structure to a temperature of about 750°C. At this temperature a solid state reaction takes place between the strontium oxide and the native silicon oxide causing the reduction of the native silicon oxide and leaving an ordered 2x1 structure with strontium, oxygen, and silicon remaining on the substrate surface. Again, this forms a template for the subsequent growth of an ordered monocrystalline oxide layer.
- an alkali earth metal oxide such as strontium oxide, strontium barium oxide, or barium oxide
- the substrate is cooled to a temperature in the range of about 200-800°C and a layer of strontium titanate is grown on the template layer by molecular beam epitaxy.
- the MBE process is initiated by opening shutters in the MBE apparatus to expose strontium, titanium and oxygen sources.
- the ratio of strontium and titanium is approximately 1 :1.
- the partial pressure of oxygen is initially set at a minimum value to grow stochiometric strontium titanate at a growth rate of about 0.3-0.5 nm per minute. After initiating growth of the strontium titanate, the partial pressure of oxygen is increased above the initial minimum value.
- the ove ⁇ ressure of oxygen causes the growth of an amo ⁇ hous silicon oxide layer at the interface between the underlying substrate and the growing strontium titanate layer.
- the growth of the silicon oxide layer results from the diffusion of oxygen through the growing strontium titanate layer to the interface where the oxygen reacts with silicon at the surface of the underlying substrate.
- the strontium titanate grows as an ordered monocrystal with the crystalline orientation rotated by 45° with respect to the ordered 2x1 crystalline structure of the underlying substrate. Strain that otherwise might exist in the strontium titanate layer because of the small mismatch in lattice constant between the silicon substrate and the growing crystal is relieved in the amo ⁇ hous silicon oxide intermediate layer.
- the monocrystalline strontium titanate is capped by a template layer that is conducive to the subsequent growth of an epitaxial layer of a desired material.
- the MBE growth of the strontium titanate monocrystalline layer can be capped by terminating the growth with 1-2 monolayers of titanium, 1-2 monolayers of titanium-oxygen or with 1-2 monolayers of strontium- oxygen.
- arsenic is deposited to form a Ti-As bond, a Ti-O-As bond or a Sr-O-As.
- gallium arsenide monocrystalline layer is subsequently introduced to the reaction with the arsenic and gallium arsenide forms.
- gallium can be deposited on the capping layer to form a Sr-O-Ga bond, and arsenic is subsequently introduced with the gallium to form the GaAs.
- FIG. 5 is a high resolution Transmission Electron Micrograph (TEM) of semiconductor material manufactured in accordance with the present invention.
- Single crystal SrTiO 3 accommodating buffer layer 24 was grown epitaxially on silicon substrate 22. During this growth process, amo ⁇ hous interfacial layer 28 is formed which relieves strain due to lattice mismatch.
- GaAs compound semiconductor layer 26 was then grown epitaxially over layer 24 using a suitable template.
- FIG. 6 illustrates an x-ray diffraction spectrum taken on a structure including GaAs compound semiconductor layer 26 grown on silicon substrate 22 using accommodating buffer layer 24.
- the peaks in the spectrum indicate that both the accommodating buffer layer 24 and GaAs compound semiconductor layer 26 are single crystal and (100) orientated.
- structures in accordance with the present invention may include an additional buffer layer inte ⁇ osed between the accommodating buffer layer and layer 26.
- the buffer layer is formed overlying the template layer before the deposition of the monocrystalline layer 26.
- the buffer layer is a compound semiconductor superlattice, such a superlattice can be deposited, by MBE for example, on the template described above.
- the buffer layer is a layer of germanium, the process above is modified to cap the strontium titanate monocrystalline layer with a final layer of either strontium or titanium and then by depositing germanium to react with the strontium or titanium. , The germanium buffer layer can then be deposited directly on this template.
- Structure 34 may be formed by growing an accommodating buffer layer, forming an amo ⁇ hous oxide layer over substrate 22, and growing layer 26 over the accommodating buffer layer, as described above.
- the accommodating buffer layer and the amo ⁇ hous oxide layer are then exposed to a laser anneal process sufficient to change the crystalline structure of the accommodating buffer layer from monocrystalline to amo ⁇ hous, thereby forming an amo ⁇ hous layer such that the combination of the amo ⁇ hous oxide layer and the now amo ⁇ hous accommodating buffer layer form a single amo ⁇ hous oxide material 36.
- the anneal process may be carried out subsequent to growth of layer 26.
- material 36 is formed by exposing the accommodating buffer layer and the amo ⁇ hous oxide layer in region 38 to laser am eal process, while shielding portion 40 from light emitted from the laser.
- Portion 40 may be shielded from the light emitted from the laser in a variety of ways.
- area 38 may be exposed to laser energy or light by rastering a light beam emitted from the laser only over portion 38.
- portion 40 may be protected from the laser beam by forming a mask over portion 40.
- Suitable mask materials include, for example, oxides such as silicon oxide, nitrides such as silicon nitrides, and metals, which are commonly used in the manufacturing of semiconductor devices.
- laser annealing techniques may be advantageous for several reasons.
- laser annealing techniques allow formation of material 36 without exposing the entire structure 34 to a heat source — only a portion 38 need be exposed to the laser beam.
- laser annealing facilitates preferential heating of various layers (e.g., layer 24) within structure 34.
- materials only absorb energy from a light beam if the energy of the beam is greater than the bandgap energy of the material.
- Equation 1 The relationship between absorbed energy wavelengths and the bandgap of a material is represented by Equation 1.
- E is the bandgap energy of a material
- h Plank's constant
- c is the speed of light
- 8 is the wavelength of light emitted from the laser.
- the maximum wavelength that will be absorbed by the GaAs is about 850 nm.
- light having wavelengths greater than about 850 nm may be used to, for example, preferably heat the silicon substrate (because the energy is not appreciably absorbed by the GaAs), which in turn provides heat to the accommodating buffer layer to cause the buffer layer to become amo ⁇ hous.
- FIG. 7 is a high resolution Transmission Electron Micrograph (TEM) of semiconductor material manufactured in accordance with the embodiment of the invention illustrated in FIG. 3.
- TEM Transmission Electron Micrograph
- a single crystal SrTiO 3 accommodating buffer layer was grown epitaxially on silicon substrate 22. During this growth process, an amo ⁇ hous interfacial layer forms as described above.
- GaAs layer 26 is formed above the accommodating buffer layer and the accommodating buffer layer is exposed to an anneal process to form amo ⁇ hous oxide material 36.
- FIG. 8 illustrates an x-ray diffraction spectrum taken on a structure including GaAs compound semiconductor layer 26 and amo ⁇ hous oxide material 36 formed on silicon substrate 22.
- the peaks in the spectrum indicate that GaAs compound semiconductor layer 26 is single crystal and (100) orientated and the lack of peaks around 40 to 50 degrees indicates that material 36 is amo ⁇ hous.
- the process described above illustrates a process for forming a semiconductor structure including a silicon substrate, an overlying oxide layer, and a monocrystalline gallium arsenide compound semiconductor layer by the process of molecular beam epitaxy.
- the process can also be carried out by the process of chemical vapor deposition (CND), metal organic chemical vapor deposition (MOCND), migration enhanced epitaxy (MEE), atomic layer epitaxy (ALE), physical vapor deposition (PND), chemical solution deposition (CSD), pulsed laser deposition (PLD), or the like.
- monocrystalline accommodating buffer layers such as alkaline earth metal titanates, zirconates, hafnates, tantalates, vanadates, ruthenates, and niobates, tin-based perovskites, lanthanum aluminate, lanthanum scandium oxide, and gadolinium oxide can also be grown.
- a similar process such as MBE, other III-N and II-NI monocrystalline compound semiconductor layers can be deposited overlying the monocrystalline oxide accommodating buffer layer.
- each of the variations of epitaxially grown materials uses an appropriate template for initiating the growth of the respective material.
- the accommodating buffer layer is an alkaline earth metal zirconate
- the oxide can be capped by a thin layer of zirconium.
- the deposition of zirconium can be followed by the deposition of arsenic or phosphorus to react with the zirconium as a precursor to depositing indium gallium arsenide, indium aluminum arsenide, or indium phosphide respectively.
- the monocrystalline oxide accommodating buffer layer is an alkaline earth metal hafnate
- the oxide layer can be capped by a thin layer of hafnium.
- hafnium is followed by the deposition of arsenic or phosphorous to react with the hafnium as a precursor to the growth of an indium gallium arsenide, indium aluminum arsenide, or indium phosphide layer, respectively.
- strontium titanate can be capped with a layer of strontium or strontium and oxygen and barium titanate can be capped with a layer of barium or barium and oxygen.
- Each of these depositions can be followed by the deposition of arsenic or phosphorus to react with the capping material to form a template for the deposition of a compound semiconductor material layer comprising indium gallium arsenide, indium aluminum arsenide, or indium phosphide.
- FIG. 9 illustrates schematically, in cross section, a device structure 50 in accordance with a further embodiment of the invention.
- Device structure 50 includes a monocrystalline semiconductor substrate 52, preferably a monocrystalline silicon wafer.
- Monocrystalline semiconductor substrate 52 includes two regions, 53 and 54.
- An electrical semiconductor component generally indicated by the dashed line 56 is formed, at least partially, in region 53.
- Electrical component 56 can be a resistor, a capacitor, an active semiconductor component such as a diode or a transistor or an integrated circuit such as a CMOS integrated circuit.
- electrical semiconductor component 56 can be a CMOS integrated circuit configured to perform digital signal processing or another function for which silicon integrated circuits are well suited.
- the electrical semiconductor component in region 53 can be formed by conventional semiconductor processing as well known and widely practiced in the semiconductor industry.
- bare silicon surfaces are highly reactive and a native silicon oxide layer can quickly form on the bare surface.
- a layer of barium or barium and oxygen is deposited onto the native oxide layer on the bare surface and is reacted with the oxidized surface to form a first template layer (not shown).
- a monocrystalline oxide material 58 is formed overlying the template layer by a process of molecular beam epitaxy. Reactants including barium, titanium and oxygen are deposited onto the template layer to form the monocrystalline oxide layer.
- the partial pressure of oxygen is__kept near the minimum necessary to fully react with the barium and titanium to form the monocrystalline barium titanate layer.
- the partial pressure of oxygen is then increased to provide an ove ⁇ ressure of oxygen and to allow oxygen to diffuse through the growing monocrystalline oxide layer.
- the oxygen diffusing through the barium titanate reacts with silicon at the surface to form an amo ⁇ hous material 57 of silicon oxide at the interface between the silicon substrate and the monocrystalline oxide.
- the step of depositing the monocrystalline oxide layer is terminated by depositing a second template layer 60, which can be 1-10 monolayers of titanium, barium, strontium, barium and oxygen, titanium and oxygen, or strontium and oxygen.
- a layer 64 of a monocrystalline semiconductor material is then deposited overlying the second template layer by a process of molecular beam epitaxy.
- the deposition of layer 64 may be initiated by depositing a layer of arsenic onto the template. This initial step is followed by depositing gallium and arsenic to form monocrystalline gallium arsenide.
- the monocrystalline titanate layer and the silicon oxide layer, which is inte ⁇ osed between substrate 52 and the titanate layer, of region 54 are exposed to a laser anneal process such that the titanate and oxide layers form an amo ⁇ hous oxide material 62.
- An additional compound semiconductor layer 66 is then epitaxially grown over layer 64, using the techniques described above in connection with layer 64, to form compound semiconductor layer 67.
- the above described anneal process can be performed after formation of additional compound semiconductor layer 66.
- forming amo ⁇ hous layer 62 prior to growth of layer 66 is advantageous because it provides a true compliant substrate for the growth of layer 66.
- Layer 66 material deposited in region 53 may include more defects than the number of defects in material 66 layer in region 54, because any strain in layers 60, 64 in region 53 are not relieved via an anneal process.
- a semiconductor component is formed, at least partially, in compound semiconductor layer 66.
- Semiconductor component 68 can be formed by processing steps conventionally used in the fabrication of gallium arsenide or other III-
- Semiconductor component 68 can be any active or passive component, and preferably is a semiconductor laser, an electromagnetic radiation (e.g., light-infra red to ultra violet radiation) emitting device, an electromagnetic radiation detector such as a photodetector, a heterojunction bipolar transistor (HBT), a high frequency MESFET, or another component that utilizes and takes advantage of the physical properties of compound semiconductor materials.
- a metallic conductor schematically indicated by the line 70 can be formed to electrically couple device 68 and device 56, thus implementing an integrated device that includes at least one component formed in the silicon substrate and one device formed in the monocrystalline compound semiconductor material layer.
- illustrative structure 50 has been described as a structure formed on a silicon substrate 52 and having a barium (or strontium) titanate layer and a gallium arsenide layer 66, similar devices can be fabricated using other monocrystalline substrates, oxide layers and other monocrystalline compound semiconductor layers as described elsewhere in this disclosure.
- FIG. 10 illustrates a semiconductor structure 72 in accordance with a further embodiment of the invention.
- Structure 72 includes a monocrystalline semiconductor substrate 74 such as a monocrystalline silicon wafer that includes a region 75 and a region 76.
- An electrical component schematically illustrated by the dashed line 78 is formed in region 75 using conventional silicon device processing techniques commonly used in the semiconductor industry.
- a monocrystalline oxide material 96 and an intermediate amo ⁇ hous silicon oxide material 98 are formed overlying substrate 74.
- a template layer 80 and subsequently a monocrystalline semiconductor layer 82 are formed overlying the monocrystalline oxide layer.
- An amo ⁇ hous oxide material 84 is then formed in region 76 by exposing the monocrystalline oxide and silicon oxide films to a laser anneal process.
- An additional monocrystalline oxide layer 86 is then formed overlying layer 82 by process steps similar to those used to form the monocrystalline oxide material described above, and an additional monocrystalline semiconductor layer 90 is formed overlying monocrystalline oxide layer 86 by process steps similar to those used to form layer 82.
- Monocrystalline oxide layer 86 may desirably be exposed to an additional laser anneal process to cause the material to become amo ⁇ hous. However, in accordance with various aspects of this embodiment, layer 86 retains its monocrystalline form.
- at least one of layers 82 and 90 are formed from a compound semiconductor material.
- a semiconductor component generally indicated by a dashed line 92 is formed at least partially in monocrystalline semiconductor layer 82.
- semiconductor component 92 may include a field effect transistor having a gate dielectric formed, in part, by monocrystalline oxide layer 86.
- monocrystalline semiconductor layer 90 can be used to implement the gate electrode of that field effect transistor.
- monocrystalline semiconductor layer 82 is formed from a group III-V compound and semiconductor component 92 is a radio frequency amplifier that takes advantage of the high mobility characteristic of group III-V component materials.
- an electrical interconnection schematically illustrated by the line 94 electrically interconnects component 78 and component 92.
- the compound semiconductor portion may include light emitting diodes, photodetectors, diodes, or the like
- the Group IV semiconductor can include digital logic, memory arrays, and most structures that can be formed in conventional MOS integrated circuits.
- a monocrystalline Group IV wafer can be used in forming only compound semiconductor electrical components over the wafer.
- the wafer is essentially a "handle" wafer used during the fabrication of the compound semiconductor electrical components within a monocrystalline compound semiconductor layer overlying the wafer. Therefore, electrical components can be formed within III-V or II- VI semiconductor materials over a wafer of at least approximately 200 millimeters in diameter and possibly at least approximately 300 millimeters.
- a relatively inexpensive "handle" wafer overcomes the fragile nature of the compound semiconductor wafers by placing them over a relatively more durable and easy to fabricate base material. Therefore, an integrated circuit can be formed such that all electrical components, and particularly all active electronic devices, can be formed within the compound semiconductor material even though the substrate itself may include a Group IV semiconductor material. Fabrication costs for compound semiconductor devices should decrease because larger substrates can be processed more economically and more readily compared to the relatively smaller and more fragile conventional compound semiconductor wafers.
Abstract
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TW507301B (en) | 2002-10-21 |
AU2001288850A1 (en) | 2002-04-15 |
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