WO2009084242A1 - 半導体基板および半導体基板の製造方法 - Google Patents
半導体基板および半導体基板の製造方法 Download PDFInfo
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- WO2009084242A1 WO2009084242A1 PCT/JP2008/004041 JP2008004041W WO2009084242A1 WO 2009084242 A1 WO2009084242 A1 WO 2009084242A1 JP 2008004041 W JP2008004041 W JP 2008004041W WO 2009084242 A1 WO2009084242 A1 WO 2009084242A1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02367—Substrates
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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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
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- H01L21/0245—Silicon, silicon germanium, germanium
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02639—Preparation of substrate for selective deposition
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/26—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, elements provided for in two or more of the groups H01L29/16, H01L29/18, H01L29/20, H01L29/22, H01L29/24, e.g. alloys
- H01L29/267—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, elements provided for in two or more of the groups H01L29/16, H01L29/18, H01L29/20, H01L29/22, H01L29/24, e.g. alloys in different semiconductor regions, e.g. heterojunctions
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- H—ELECTRICITY
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/70—Bipolar devices
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Definitions
- the present invention relates to a semiconductor substrate and a method for manufacturing the semiconductor substrate.
- the present invention particularly relates to a semiconductor substrate in which a crystalline thin film having excellent crystallinity is formed on an inexpensive silicon substrate and a method for manufacturing the semiconductor substrate.
- GaAs gallium arsphide
- various high-performance electronic devices have been developed using heterojunctions.
- a high-performance electronic device since the quality of crystallinity affects device characteristics, a high-quality crystal thin film is required.
- GaAs-based device GaAs or Ge or the like whose lattice constant is very close to that of GaAs is selected as a substrate because of a request for lattice matching at a hetero interface.
- Non-Patent Document 1 describes a technique for forming a high-quality Ge epitaxial growth layer (hereinafter sometimes referred to as a Ge epilayer) on a Si substrate.
- a Ge epilayer a high-quality Ge epitaxial growth layer
- the Ge epi layer is subjected to cycle thermal annealing to obtain an average dislocation density of 2.3 ⁇ 10 6 cm ⁇ 2.
- cycle thermal annealing to obtain an average dislocation density of 2.3 ⁇ 10 6 cm ⁇ 2.
- Hsin-Chiao Luan et. al. “High-quality Ge epilayers on Si with low threading-dislocation density”, APPLIED PHYSICS LETTERS, VOLUME 75, NUMBER 19, 8 NOVEMBER 1999.
- a substrate that can be lattice-matched to GaAs such as a GaAs substrate or a Ge substrate is selected as described above.
- a substrate that can be lattice-matched to GaAs such as a GaAs substrate or a Ge substrate, is expensive, increasing the cost of the device.
- these boards do not have sufficient heat dissipation characteristics, and there is a possibility that the formation density of devices will be suppressed or the devices may be used within the range where heat dissipation can be managed for a sufficient thermal design. .
- an object of one aspect of the present invention is to provide a “semiconductor substrate, method for manufacturing a semiconductor substrate, and electronic device” that can solve the above-described problems. This object is achieved by a combination of features described in the independent claims.
- the dependent claims define further advantageous specific examples of the present invention.
- a single crystal Si substrate an insulating layer formed on the substrate and having an opening region, and Ge grown epitaxially on the substrate in the opening region.
- a GaAs layer epitaxially grown on the Ge layer, wherein the Ge layer is introduced at a first temperature at which a substrate can be introduced into a CVD reaction chamber that can be in an ultra-high vacuum reduced pressure state, and the source gas can be thermally decomposed.
- the first epitaxial growth is performed, the second epitaxial growth is performed at a second temperature higher than the first temperature, and the epitaxial layer on which the first and second epitaxial growth is performed is the first temperature at a third temperature that does not reach the melting point of Ge.
- a semiconductor substrate formed by performing annealing and performing second annealing at a fourth temperature lower than the third temperature is provided.
- the Ge layer may be formed by repeating the first annealing and the second annealing a plurality of times, and the insulating layer may be a silicon oxide layer.
- a single crystal Si substrate an insulating layer having an opening formed through the substrate in a direction substantially perpendicular to the main surface of the substrate and exposing the substrate, and the opening
- a Ge layer crystal-grown on the substrate inside the substrate, and a GaAs layer epitaxially grown on the Ge layer, wherein the Ge layer is placed in a CVD reaction chamber that can be in an ultra-high vacuum reduced pressure state.
- a substrate is introduced, a first epitaxial growth is performed at a first temperature at which the source gas can be thermally decomposed, a second epitaxial growth is performed at a second temperature higher than the first temperature, and the first and second epitaxial growths are performed.
- a semiconductor substrate formed by performing a first annealing at a third temperature that does not reach the melting point of Ge, and performing a second annealing at a fourth temperature lower than the third temperature.
- the Ge layer may be formed by performing at least one annealing selected from the first annealing and the second annealing in an atmosphere containing hydrogen.
- the Ge layer may be formed by selective crystal growth in the opening using a CVD method in which a gas containing a halogen element is used as a source gas.
- the arithmetic average roughness of the GaAs layer may be 0.02 ⁇ m or less.
- the insulating layer may be a silicon oxide layer.
- the insulating layer includes a plurality of the openings, and the gap between one of the plurality of openings and another opening adjacent to the one opening is higher than the upper surface of the insulating layer.
- a raw material adsorption part that adsorbs the raw material of the GaAs layer at a high adsorption rate may be included.
- the semiconductor substrate includes a plurality of the insulating layers, and any one of the plurality of insulating layers between one insulating layer of the plurality of insulating layers and another insulating layer adjacent to the one insulating layer.
- a raw material adsorption portion that adsorbs the raw material of the GaAs layer at a higher adsorption rate than the upper surface of the GaAs layer may be included.
- the raw material adsorption portion may be a groove reaching the substrate.
- the width of the groove may be 20 ⁇ m or more and 500 ⁇ m or less.
- the semiconductor substrate may include a plurality of the raw material adsorption portions, and each of the plurality of raw material adsorption portions may be arranged at equal intervals.
- the bottom area of the opening may be 1 mm 2 or less.
- a bottom area of the opening may be 1600 ⁇ m 2 or less.
- a bottom area of the opening may be 900 ⁇ m 2 or less.
- a bottom surface of the opening may be a rectangle, and a long side of the rectangle may be 80 ⁇ m or less.
- a bottom surface of the opening may be a rectangle, and a long side of the rectangle may be 40 ⁇ m or less.
- a main surface of the substrate is a (100) surface
- a bottom surface of the opening is a square or a rectangle, and a direction of at least one side of the square or the rectangle is ⁇ 010> on the main surface.
- the direction may be substantially parallel to any one direction selected from the group consisting of a direction, a ⁇ 0-10> direction, a ⁇ 001> direction, and a ⁇ 00-1> direction.
- a main surface of the substrate is a (111) surface
- a bottom surface of the opening is a hexagon
- a direction of at least one side of the hexagon is a ⁇ 1-10> direction on the main surface.
- ⁇ 110> direction, ⁇ 0-11> direction, ⁇ 01-1> direction, ⁇ 10-1> direction, and ⁇ 101> direction and substantially parallel to any one direction selected from the group consisting of It may be.
- the Miller index indicating the plane or direction of the crystal, when the index is negative, a notation method in which a bar is added on the number is common. However, when the index becomes negative, in this specification, it is expressed as a negative number for convenience.
- a plane that intersects each of the a-axis, b-axis, and c-axis of the unit cell with 1, -2, and 3 is represented as a (1-23) plane. The same applies to the Miller index in the direction.
- a substrate on which an insulating layer having an insulating layer is formed is introduced into a CVD reaction chamber that can be brought into an ultra-high vacuum decompression state, and the substrate gas is introduced into the CVD reaction chamber at a first temperature at which the source gas can be thermally decomposed.
- the third embodiment may further include a step of repeating the step of performing the annealing at the third temperature and the step of performing the annealing at the fourth temperature a plurality of times, and the insulating layer may be a silicon oxide layer.
- a step of forming an insulating layer on a single crystal Si substrate, and a step of patterning the insulating layer to form an opening in the insulating layer exposing the substrate introducing the substrate including the insulating layer in which the opening is formed into a CVD reaction chamber that can be in an ultra-high vacuum reduced pressure state, introducing a source gas into the CVD reaction chamber, and introducing the source gas into the CVD reaction chamber Heating the substrate to a first temperature capable of pyrolysis to selectively form a first epitaxial layer of Ge on the substrate exposed in the opening; and introducing a source gas into the CVD reaction chamber; Heating the substrate to a second temperature higher than the first temperature to form a second epitaxial layer of Ge on the first epitaxial layer; the first epitaxial layer and the second epitaxial layer; Annealing the axial layer at a third temperature that does not reach the melting point of Ge, annealing the first epitaxial layer and the second epitaxial layer at a fourth
- the third temperature and the fourth temperature may be 680 ° C. or higher and lower than 900 ° C.
- the step of annealing at the third temperature may anneal the Ge layer in an atmosphere containing hydrogen.
- the step of annealing at the fourth temperature may anneal the Ge layer in an atmosphere containing hydrogen.
- the step of selectively forming the first epitaxial layer of Ge selectively crystallizes the Ge layer in the opening by a CVD method under a pressure of 0.1 Pa to 100 Pa. It may be grown.
- the step of selectively forming the second epitaxial layer of Ge selectively crystallizes the Ge layer in the opening by a CVD method under a pressure of 0.1 Pa to 100 Pa. It may be grown.
- the step of selectively forming the first Ge epitaxial layer includes selecting the Ge layer as the opening by a CVD method in an atmosphere containing a gas containing a halogen element as a source gas. Alternatively, crystal growth may be performed.
- the step of selectively forming the Ge second epitaxial layer includes selecting the Ge layer as the opening by a CVD method in an atmosphere containing a gas containing a halogen element as a source gas. Alternatively, crystal growth may be performed.
- the step of epitaxially growing the GaAs layer may be performed by crystal growth of the GaAs layer at a growth rate of 1 nm / min to 300 nm / min.
- a cross-sectional example of the semiconductor substrate 101 of this embodiment is shown together with an HBT formed in an element formation region.
- the cross-sectional example in the manufacture process of the semiconductor substrate 101 is shown.
- the cross-sectional example in the manufacture process of the semiconductor substrate 101 is shown.
- the cross-sectional example in the manufacture process of the semiconductor substrate 101 is shown.
- the cross-sectional example in the manufacture process of the semiconductor substrate 101 is shown.
- the cross-sectional example in the manufacture process of the semiconductor substrate 101 is shown.
- the cross-sectional shape of the Ge layer 120 which has not been annealed is shown.
- the cross-sectional shape of the Ge layer 120 annealed at 700 degreeC is shown.
- the cross-sectional shape of the Ge layer 120 annealed at 800 degreeC is shown.
- the cross-sectional shape of the Ge layer 120 annealed at 850 degreeC is shown.
- the cross-sectional shape of the Ge layer 120 annealed at 900 degreeC is shown.
- the average value of the film thickness of the GaAs layer 124 in Example 1 is shown.
- the coefficient of variation of the film thickness of the GaAs layer 124 in Example 1 is shown.
- the average value of the film thickness of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 2 is shown.
- the electron micrograph of the GaAs layer 124 in Example 3 is shown.
- the electron micrograph of the GaAs layer 124 in Example 3 is shown.
- the electron micrograph of the GaAs layer 124 in Example 3 is shown.
- the electron micrograph of the GaAs layer 124 in Example 3 is shown.
- the electron micrograph of the GaAs layer 124 in Example 4 is shown.
- the electron micrograph of the GaAs layer 124 in Example 4 is shown.
- the electron micrograph of the GaAs layer 124 in Example 4 is shown.
- the electron micrograph of the semiconductor substrate in Example 5 is shown.
- the laser microscope image of the HBT element in Example 6 is shown.
- the laser microscope image of the electronic device in Example 7 is shown.
- the relationship between the electrical characteristics of the HBT element and the area of the opening region is shown.
- FIG. 1 shows a cross-sectional example of a semiconductor substrate 101 of this embodiment together with an HBT (heterojunction bipolar transistor) formed in an element formation region.
- the semiconductor substrate 101 includes a single crystal Si wafer 102, an insulating layer 104, a Ge layer 120, and a GaAs layer 124.
- HBT is formed as an electronic element.
- the GaAs layer 124 On the surface of the GaAs layer 124, a collector mesa, an emitter mesa, and a base mesa of the HBT are formed. A collector electrode 108, an emitter electrode 110, and a base electrode 112 are formed on the surfaces of the collector mesa, emitter mesa, and base mesa through contact holes.
- the GaAs layer 124 includes a collector layer, an emitter layer, and a base layer of HBT.
- a collector layer As a collector layer, a carrier concentration of 3.0 ⁇ 10 18 cm -3, and n + GaAs layer having a thickness of 500 nm, the carrier concentration of 1.0 ⁇ 10 16 cm -3, a thickness of 500 nm n - and GaAs layer, A laminated film in which the layers are laminated in order from the substrate direction can be exemplified.
- An example of the base layer is a p ⁇ GaAs layer having a carrier concentration of 5.0 ⁇ 10 19 cm ⁇ 3 and a film thickness of 50 nm.
- the Si wafer 102 may be an example of a single crystal Si substrate.
- a commercially available Si wafer can be used as the Si wafer 102.
- the insulating layer 104 is formed on the Si wafer 102 and has an opening region. The open area may expose the Si wafer 102.
- a silicon oxide layer can be exemplified.
- the insulating layer 104 has an opening in the opening region.
- the “bottom shape” of the opening means the shape of the opening on the substrate side surface of the layer in which the opening is formed.
- the bottom shape of the opening may be referred to as the bottom surface of the opening.
- the “planar shape” of the covering region means a shape when the covering region is projected onto the main surface of the substrate.
- the area of the planar shape of the covering region may be referred to as the area of the covering region.
- the surface of the Si wafer 102 may be an example of the main surface of the substrate.
- Bottom area of the opening may be at 0.01 mm 2 or less, preferably may be at 1600 .mu.m 2 or less, more preferably be at 900 .mu.m 2 or less.
- the area is 0.01 mm 2 or less, the time required for the annealing treatment of the Ge layer formed inside the opening can be shortened as compared with the case where the area is larger than 0.01 mm 2 .
- the difference in thermal expansion coefficient between the functional layer and the substrate is large, local warpage tends to occur in the functional layer due to the thermal annealing treatment. Even in such a case, it is possible to suppress the occurrence of crystal defects in the functional layer due to the warpage by setting the bottom area of the opening to 0.01 mm 2 or less.
- a high-performance device can be manufactured using a functional layer formed inside the opening.
- the area is 900 ⁇ m 2 or less, the device can be manufactured with high yield.
- the bottom area of the opening may be 25 ⁇ m 2 or more.
- the ratio of the bottom area of the opening to the area of the covering region may be 0.01% or more. If the ratio is less than 0.01%, the growth rate of the crystal becomes unstable when the crystal is grown inside the opening.
- the bottom area of the opening is the sum of the bottom areas of the plurality of openings included in the covering region. Means.
- the length of one side of the bottom shape may be 100 ⁇ m or less, preferably 80 ⁇ m or less, more preferably 40 ⁇ m or less, Preferably, it may be 30 ⁇ m or less.
- the time required for the annealing treatment of the Ge layer formed inside the opening is larger than when the length of one side of the bottom shape is larger than 100 ⁇ m. Can be shortened.
- the difference in thermal expansion coefficient between the functional layer and the substrate is large, the occurrence of crystal defects in the functional layer can be suppressed.
- a high-performance device can be formed using a functional layer formed inside the opening.
- the device can be manufactured with high yield.
- the length of the one side may be the length of the long side.
- One opening may be formed inside one covering region. Thereby, when the crystal is epitaxially grown inside the opening, the growth rate of the crystal can be stabilized.
- a plurality of openings may be formed inside one covering region. In this case, it is preferable that a plurality of openings are arranged at equal intervals. Thereby, when the crystal is epitaxially grown inside the opening, the growth rate of the crystal can be stabilized.
- the direction of at least one side of the polygon may be substantially parallel to one of the crystallographic plane orientations of the main surface of the substrate.
- the crystallographic orientation may be selected such that a stable surface is formed on the side surface of the crystal growing inside the opening.
- substantially parallel includes the case where the direction of one side of the polygon and one of the crystallographic plane orientations of the substrate are slightly inclined from parallel. The magnitude of the inclination may be 5 ° or less. Thereby, the disorder
- the main surface of the substrate may be a (100) surface, a (110) surface, a (111) surface, or a surface equivalent to these.
- the main surface of the substrate may be slightly inclined from the crystallographic plane orientation. That is, the substrate may have an off angle.
- the magnitude of the inclination may be 10 ° or less.
- the magnitude of the inclination may be preferably 0.05 ° to 6 °, more preferably 0.3 ° to 6 °.
- the main surface of the substrate may be the (100) plane or the (110) plane or a plane equivalent thereto. As a result, the four-fold symmetric side surface is likely to appear in the crystal.
- the insulating layer 104 is formed on the (100) surface of the surface of the Si wafer 102, an opening region having a square or rectangular bottom shape is formed in the insulating layer 104, and the Ge layer 120 is formed inside the opening region.
- the direction of at least one side of the bottom shape of the opening region is selected from the group consisting of the ⁇ 010> direction, ⁇ 0-10> direction, ⁇ 001> direction, and ⁇ 00-1> direction of the Si wafer 102. It may be substantially parallel to any one direction. Thereby, a stable surface appears on the side surface of the GaAs crystal.
- an insulating layer 104 is formed on the (111) plane of the surface of the Si wafer 102, an opening region having a hexagonal bottom shape is formed in the insulating layer 104, and a Ge layer is formed inside the opening region.
- the 120 and the GaAs layer 124 are formed will be described as an example.
- at least one side of the bottom surface shape of the opening region is the ⁇ 1-10> direction, ⁇ 110> direction, ⁇ 0-11> direction, ⁇ 01-1> direction, ⁇ 10-1> of the Si wafer 102.
- the direction may be substantially parallel to any one direction selected from the group consisting of a direction and a ⁇ 101> direction.
- the planar shape of the opening region may be a regular hexagon.
- a GaN crystal that is a hexagonal crystal can be formed instead of a GaAs crystal.
- a plurality of insulating layers 104 may be formed on the Si wafer 102. As a result, a plurality of covered regions are formed on the Si wafer 102.
- a raw material adsorption portion that adsorbs the raw material of the Ge layer 120 or the GaAs layer 124 may be provided.
- Each of the plurality of insulating layers 104 may be surrounded by the raw material adsorption portion. Thereby, when the crystal is epitaxially grown inside the opening, the growth rate of the crystal can be stabilized.
- the Ge layer or the functional layer may be an example of the crystal.
- each insulating layer 104 may have a plurality of openings.
- a raw material adsorbing portion may be included between one of the plurality of openings and another opening adjacent to the one opening.
- each of the plurality of raw material adsorption units may be arranged at equal intervals.
- the raw material adsorption portion may be the surface of the Si wafer 102.
- the raw material adsorption part may be a groove reaching the Si wafer 102.
- the width of the groove may be 20 ⁇ m or more and 500 ⁇ m or less.
- the raw material adsorption portions may be arranged at equal intervals.
- the raw material adsorption portion may be a region where crystal growth occurs.
- a source gas containing constituent elements of a thin film crystal to be formed is supplied onto a substrate, and the source gas in the gas phase or the substrate surface is supplied.
- a thin film is formed by the chemical reaction.
- the source gas supplied into the reaction apparatus generates a reaction intermediate (hereinafter sometimes referred to as a precursor) by a gas phase reaction.
- the produced reaction intermediate diffuses in the gas phase and is adsorbed on the substrate surface.
- the reaction intermediate adsorbed on the substrate surface diffuses on the substrate surface and is deposited as a solid film.
- the precursor that diffuses the surface of the covering region by arranging a raw material adsorption part between two adjacent insulating layers 104 or by surrounding the insulating layer 104 with the raw material adsorption part is, for example, a raw material Captured, adsorbed or fixed to the adsorption part. Thereby, when the crystal is epitaxially grown inside the opening, the growth rate of the crystal can be stabilized.
- the precursor may be an example of a crystal raw material.
- a coating region having a predetermined size is arranged on the surface of the Si wafer 102, and the coating region is surrounded by the surface of the Si wafer 102.
- a crystal is grown inside the opening region by MOCVD, a part of the precursor reaching the surface of the Si wafer 102 grows on the surface of the Si wafer 102. In this way, a part of the precursor is consumed on the surface of the Si wafer 102, so that the growth rate of crystals formed in the opening is stabilized.
- the raw material adsorption portion can be formed by depositing an amorphous semiconductor or a semiconductor polycrystal on the surface of the insulating layer 104 by an ion plating method, a sputtering method, or the like.
- the raw material adsorption portion may be disposed between the insulating layer 104 and the adjacent insulating layer 104, or may be included in the insulating layer 104. Further, the same effect can be obtained by arranging a region where the diffusion of the precursor is inhibited between two adjacent coating regions, or by surrounding the coating region with a region where the diffusion of the precursor is inhibited. Is obtained.
- the distance between two adjacent insulating layers 104 may be 20 ⁇ m or more. Thereby, the growth rate of the crystal is further stabilized.
- the distance between two adjacent insulating layers 104 is the shortest distance between a point on the outer periphery of an insulating layer 104 and a point on the outer periphery of another insulating layer 104 adjacent to the insulating layer 104. Show.
- the plurality of insulating layers 104 may be arranged at equal intervals. In particular, when the distance between two adjacent insulating layers 104 is less than 10 ⁇ m, the crystal growth rate in the opening can be stabilized by arranging the plurality of insulating layers 104 at equal intervals.
- the Si wafer 102 may be a high-resistance wafer that does not contain impurities, or may be a medium-resistance or low-resistance wafer that contains p-type or n-type impurities.
- the Ge layer 120 may be Ge containing no impurities, or may contain p-type or n-type impurities.
- the Ge layer 120 is epitaxially grown on the Si wafer 102 in the opening region.
- the Ge layer 120 may be selectively epitaxially grown on the Si wafer 102 in the opening region.
- the Ge layer 120 is formed by annealing after epitaxial growth as follows.
- a second temperature at a second temperature higher than the first temperature is obtained.
- Epitaxial growth is performed.
- the second annealing is performed at a fourth temperature lower than the third temperature. .
- the first annealing and the second annealing can be repeated a plurality of times. Note that after annealing the Ge layer 120, the surface of the Ge layer 120 may be processed by supplying a gas containing phosphine to the surface of the Ge layer 120.
- the Ge layer 120 may be annealed at less than 900 ° C., preferably 850 ° C. or less. Thereby, the flatness of the surface of the Ge layer 120 can be maintained. The flatness of the surface of the Ge layer 120 becomes particularly important when another layer is stacked on the surface of the Ge layer 120.
- the Ge layer 120 may be annealed at 680 ° C. or higher, preferably 700 ° C. or higher. Thereby, the density of crystal defects in the Ge layer 120 can be reduced.
- the Ge layer 120 may be annealed under conditions of 680 ° C. or higher and lower than 900 ° C.
- FIG. 7 to 11 show the relationship between the annealing temperature and the flatness of the Ge layer 120.
- FIG. FIG. 7 shows a cross-sectional shape of the Ge layer 120 that is not annealed.
- 8, 9, 10 and 11 show the cross-sectional shapes of the Ge layer 120 when annealing is performed at 700 ° C., 800 ° C., 850 ° C. and 900 ° C., respectively.
- the cross-sectional shape of the Ge layer 120 was observed with a laser microscope.
- the vertical axis indicates the distance in the direction perpendicular to the main surface of the Si wafer 102 and indicates the film thickness of the Ge layer 120.
- the horizontal axis of each figure shows the distance in the direction parallel to the main surface of the Si wafer 102.
- the Ge layer 120 was formed by the following procedure. First, an insulating layer 104 of SiO 2 layer was formed on the surface of the Si wafer 102 by a thermal oxidation method, and a covering region and an opening region were formed in the insulating layer 104. As the Si wafer 102, a commercially available single crystal Si substrate was used. The planar shape of the covering region was a square having a side length of 400 ⁇ m. Next, the Ge layer 120 was selectively grown inside the opening region by the CVD method.
- the flatness of the surface of the Ge layer 120 is better as the annealing temperature is lower.
- the annealing temperature is less than 900 ° C., the surface of the Ge layer 120 exhibits excellent flatness.
- the Ge layer 120 may be annealed in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or a hydrogen atmosphere.
- an atmosphere containing hydrogen the density of crystal defects in the Ge layer 120 can be reduced while maintaining the surface state of the Ge layer 120 in a smooth state.
- the Ge layer 120 may be annealed under conditions that satisfy the temperature and time at which crystal defects can move.
- annealing is performed on the Ge layer 120, crystal defects in the Ge layer 120 move inside the Ge layer 120, and for example, the interface between the Ge layer 120 and the insulating layer 104, the surface of the Ge layer 120, or Ge Captured by a gettering sink inside layer 120.
- the interface between the Ge layer 120 and the insulating layer 104, the surface of the Ge layer 120, or the gettering sink inside the Ge layer 120 is an example of a defect capturing unit that captures crystal defects that can move inside the Ge layer 120. It's okay.
- the defect trapping part may be a crystal interface or surface, or a physical scratch.
- the defect trapping portion may be disposed within a distance that the crystal defect can move at the annealing temperature and time.
- the Ge layer 120 may be an example of a seed layer that provides a seed surface for the functional layer.
- Another example of the seed layer is Si x Ge 1-x (where 0 ⁇ x ⁇ 1).
- the annealing may be a two-step annealing in which high-temperature annealing at 800 to 900 ° C. for 2 to 10 minutes and low-temperature annealing at 680 to 780 ° C. for 2 to 10 minutes are repeatedly performed.
- the Ge layer 120 may be selectively grown in the opening region.
- the Ge layer 120 can be formed by, for example, a CVD method or an MBE method (molecular beam epitaxy method).
- Raw material gas may be GeH 4.
- the Ge layer 120 may be formed by a CVD method under a pressure of 0.1 Pa to 100 Pa. This makes the growth rate of the Ge layer 120 less susceptible to the area of the opening region. As a result, for example, the uniformity of the film thickness of the Ge layer 120 is improved. In this case, the deposition of Ge crystals on the surface of the insulating layer 104 can be suppressed.
- the Ge layer 120 may be formed by a CVD method in an atmosphere containing a gas containing a halogen element as a source gas.
- the gas containing a halogen element may be hydrogen chloride gas or chlorine gas.
- the present invention is not limited to this.
- another layer may be disposed between the Ge layer 120 and the Si wafer 102.
- the other layer may be a single layer or may include a plurality of layers.
- the Ge layer 120 may be formed by the following procedure. First, a seed crystal is formed at a low temperature.
- the seed crystal may be Si x Ge 1-x (where 0 ⁇ x ⁇ 1).
- the growth temperature of the seed crystal may be 330 ° C. or higher and 450 ° C. or lower. After that, the temperature of the Si wafer 102 on which the seed crystal is formed is raised to a predetermined temperature, and then the Ge layer 120 may be formed.
- the GaAs layer 124 is formed by epitaxial growth on the Ge layer 120.
- the GaAs layer 124 can be formed directly on the Ge layer 120.
- the GaAs layer 124 can also be formed on the Ge layer 120 with another layer therebetween.
- the GaAs layer 124 may have an arithmetic average roughness (hereinafter also referred to as Ra value) of 0.02 ⁇ m or less, preferably 0.01 ⁇ m or less.
- Ra value is an index representing the surface roughness and can be calculated based on JIS B0601-2001.
- the Ra value can be calculated by folding a roughness curve of a certain length from the center line and dividing the area obtained by the roughness curve and the center line by the measured length.
- the growth rate of the GaAs layer 124 may be 300 nm / min or less, preferably 200 nm / min or less, and more preferably 60 nm / min or less. Thereby, the Ra value of the GaAs layer 124 can be 0.02 ⁇ m or less. On the other hand, the growth rate of the GaAs layer 124 may be 1 nm / min or more, and preferably 5 nm / min or more. As a result, a high-quality GaAs layer 124 can be obtained without sacrificing productivity.
- the GaAs layer 124 may be crystal-grown at a growth rate of 1 nm / min to 300 nm / min.
- an intermediate layer may be disposed between the Ge layer 120 and the GaAs layer 124.
- the intermediate layer may be a single layer or may include a plurality of layers.
- the intermediate layer may be formed at 600 ° C. or lower, preferably 550 ° C. or lower. Thereby, the crystallinity of the GaAs layer 124 is improved.
- the intermediate layer may be formed at 400 ° C. or higher.
- the intermediate layer may be formed at 400 ° C. or higher and 600 ° C. or lower. Thereby, the crystallinity of the GaAs layer 124 is improved.
- the intermediate layer may be a GaAs layer formed at a temperature of 600 ° C. or lower, preferably 550 ° C. or lower.
- the GaAs layer 124 may be formed by the following procedure. First, an intermediate layer is formed on the surface of the Ge layer 120. The growth temperature of the intermediate layer may be 600 ° C. or less. Thereafter, the temperature of the Si wafer 102 on which the intermediate layer is formed is raised to a predetermined temperature, and then the GaAs layer 124 may be formed.
- FIG. 2 to 6 show cross-sectional examples in the manufacturing process of the semiconductor substrate 101.
- a Si wafer 102 is prepared, and a silicon oxide film 130, for example, serving as an insulating layer is formed on the surface of the Si wafer 102.
- the silicon oxide film 130 can be formed using, for example, a thermal oxidation method.
- the film thickness of the silicon oxide film 130 can be set to 1 ⁇ m, for example.
- the insulating layer 104 is formed by patterning the silicon oxide film 130. By the formation of the insulating layer 104, an opening region is formed. For patterning, for example, a photolithography method can be used.
- a Ge layer 120 is epitaxially grown in the opening region.
- the epitaxial growth of the Ge layer 120 is performed as follows. First, the Si wafer 102 is introduced into a CVD reaction chamber that can be brought into an ultra-high vacuum pressure reduction state, a source gas is introduced into the CVD reaction chamber, and the substrate is heated to a first temperature at which the source gas can be thermally decomposed.
- a Ge first epitaxial layer is selectively formed on the Si wafer 102 exposed in the opening region.
- a source gas is introduced into the CVD reaction chamber and the substrate is heated to a second temperature higher than the first temperature to form a Ge second epitaxial layer on the first epitaxial layer.
- GeH 4 can be used as the source gas.
- thermal annealing is performed on the epitaxially grown Ge layer 120.
- Thermal annealing is performed as follows. First, the first and second epitaxial layers are annealed at a third temperature that does not reach the melting point of Ge.
- the first and second epitaxial layers are annealed at a fourth temperature lower than the third temperature.
- the Ge layer 120 selectively epitaxially grown in the opening region is formed.
- Such two-step annealing can be repeated a plurality of times.
- a temperature of 900 ° C. and a time of 10 minutes can be exemplified.
- An example of annealing conditions at the fourth temperature is a temperature and time condition of 780 ° C. for 10 minutes.
- An example of the number of repetitions is 10 times.
- a gas containing phosphine may be supplied to the surface of the Ge layer 120 to treat the surface of the Ge layer 120.
- the crystal defects existing at the stage of epitaxial growth can be moved to the edge of the Ge layer 120 by annealing, and the crystal defects of the Ge layer 120 are eliminated by eliminating the crystal defects in the edge of the Ge layer 120.
- the density can be made extremely low. Thereby, defects due to the substrate material of the epitaxial thin film to be formed later can be reduced, and as a result, the performance of the electronic element formed in the GaAs layer 124 can be improved. Further, even if the thin film is of a type that cannot be directly grown on the silicon substrate due to lattice mismatch, a high-quality crystalline thin film can be formed using the Ge layer 120 having excellent crystallinity as the substrate material.
- the Ge layer 120 after annealing can be held at a high temperature, and a gas containing PH 3 (phosphine) on the surface can be supplied.
- a gas containing PH 3 (phosphine) on the surface can be supplied.
- PH 3 phosphine
- the crystal quality of the GaAs layer 124 grown thereon can be improved.
- As preferable processing temperature 500 degreeC or more and 900 degrees C or less can be illustrated. When the temperature is lower than 500 ° C., the treatment effect does not appear, and when the temperature is higher than 900 ° C., the Ge layer 120 is deteriorated, which is not preferable.
- a more preferable treatment temperature is 600 ° C. or higher and 800 ° C. or lower.
- a source gas capable of forming a GaAs layer is introduced into the CVD reaction chamber, and the GaAs layer 124 is epitaxially grown in contact with the Ge layer 120 whose surface has been treated.
- the MOCVD method or the MBE method can be used.
- the source gas TM-Ga (trimethylgallium) or AsH 3 (arsine) can be used.
- the growth temperature include 600 ° C. to 650 ° C.
- the semiconductor substrate 101 shown in FIG. 1 is obtained.
- the semiconductor substrate 101 of this embodiment was able to be manufactured by the method described above.
- the Ge layer 120 is selectively grown in the opening region partitioned by the insulating layer 104, and the Ge layer 120 is subjected to two-stage annealing a plurality of times to improve the crystallinity of the Ge layer 120.
- the semiconductor substrate 101 having the GaAs layer 124 with excellent crystallinity was obtained. Since the semiconductor wafer 101 employs the Si wafer 102, the semiconductor substrate 101 can be manufactured at low cost, and the heat generated by the electronic elements formed on the GaAs layer 124 can be efficiently exhausted.
- Example 1 A semiconductor substrate provided with the Si wafer 102, the insulating layer 104, the Ge layer 120, and the GaAs layer 124 is manufactured, and the growth rate of the crystal growing inside the opening formed in the insulating layer 104, the coverage region The relationship between the size and the size of the opening was investigated. The experiment was performed by changing the planar shape of the covering region formed on the insulating layer 104 and the bottom shape of the opening, and measuring the film thickness of the GaAs layer 124 grown for a certain period of time.
- a covering region and an opening were formed on the surface of the Si wafer 102 by the following procedure.
- the Si wafer 102 a commercially available single crystal Si substrate was used.
- An SiO 2 layer was formed as an example of the insulating layer 104 on the surface of the Si wafer 102 by thermal oxidation.
- SiO 2 layer was formed in a predetermined size. Three or more SiO 2 layers having a predetermined size were formed. At this time, the planar shape of the SiO 2 layer having a predetermined size was designed to be a square having the same size. Further, an opening having a predetermined size was formed in the center of the square SiO 2 layer by etching. At this time, the center of the square SiO 2 layer was designed so that the center of the opening coincided. One opening was formed for each of the square SiO 2 layers. In the present specification, the length of one side of the square SiO 2 layer may be referred to as the length of one side of the covered region.
- the Ge layer 120 was selectively grown inside the opening by the CVD method.
- GeH 4 was used as the source gas.
- the flow rate of the source gas and the film formation time were set to predetermined values, respectively.
- the GaAs layer 124 was grown by MOCVD.
- the GaAs layer 124 was epitaxially grown on the surface of the Ge layer 120 inside the opening under the conditions of 620 ° C. and 8 MPa. Trimethyl gallium and arsine were used as source gases.
- the flow rate of the source gas and the film formation time were set to predetermined values, respectively.
- the thickness of the GaAs layer 124 was measured.
- the film thickness of the GaAs layer 124 is measured by measuring the film thickness at three measurement points of the GaAs layer 124 with a needle-type step gauge (manufactured by KLA Tencor, Surface Profiler P-10). Calculated by averaging. At this time, the standard deviation of the film thickness at the three measurement points was also calculated.
- the film thickness is obtained by directly measuring the film thickness at three measurement points of the GaAs layer 124 by a cross-sectional observation method using a transmission electron microscope or a scanning electron microscope, and averaging the film thicknesses at the three positions. You may calculate by.
- the thickness of the GaAs layer 124 was measured by changing the bottom shape of the opening when the length of one side of the covering region was set to 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, or 500 ⁇ m. .
- the bottom shape of the opening was tested in three ways: a square with a side of 10 ⁇ m, a square with a side of 20 ⁇ m, and a rectangle with a short side of 30 ⁇ m and a long side of 40 ⁇ m.
- the plurality of square SiO 2 layers are integrally formed.
- the covering regions having a side length of 500 ⁇ m are not arranged at intervals of 500 ⁇ m, but for the sake of convenience, the length of one side of the covering region is represented as 500 ⁇ m.
- the distance between two adjacent covering regions is expressed as 0 ⁇ m.
- Example 1 The experimental results of Example 1 are shown in FIGS.
- FIG. 12 shows the average value of the film thickness of the GaAs layer 124 in each case of Example 1.
- FIG. 13 shows the coefficient of variation of the film thickness of the GaAs layer 124 in each case of Example 1.
- FIG. 12 shows the relationship between the growth rate of the GaAs layer 124 and the size of the covered region and the size of the opening.
- the vertical axis represents the film thickness [ ⁇ ] of the GaAs layer 124 grown during a certain time
- the horizontal axis represents the length [ ⁇ m] of one side of the covered region.
- an approximate value of the growth rate of the GaAs layer 124 can be obtained by dividing the film thickness by the time.
- the rhombus plot indicates experimental data when the bottom shape of the opening is a square having a side of 10 ⁇ m
- the square plot indicates experimental data when the bottom shape of the opening is a square having a side of 20 ⁇ m.
- a triangular plot shows experimental data when the bottom shape of the opening is a rectangle having a long side of 40 ⁇ m and a short side of 30 ⁇ m.
- FIG. 12 shows that the growth rate monotonously increases as the size of the covered region increases. Further, it can be seen that the growth rate increases almost linearly when the length of one side of the covering region is 400 ⁇ m or less, and there is little variation due to the bottom shape of the opening. On the other hand, when the length of one side of the covering region is 500 ⁇ m, the growth rate increases rapidly compared to the case where the length of one side of the covering region is 400 ⁇ m or less, and the variation due to the bottom shape of the opening is large.
- FIG. 13 shows the relationship between the variation coefficient of the growth rate of the GaAs layer 124 and the distance between two adjacent coating regions.
- the variation coefficient is a ratio of the standard deviation to the average value, and can be calculated by dividing the standard deviation of the film thickness at the three measurement points by the average value of the film thickness.
- the vertical axis represents the coefficient of variation of the film thickness [ ⁇ ] of the GaAs layer 124 grown during a certain time
- the horizontal axis represents the distance [ ⁇ m] between adjacent coating regions.
- FIG. 13 shows experimental data when the distance between two adjacent coating regions is 0 ⁇ m, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m and 450 ⁇ m.
- the rhombus plot shows experimental data when the bottom shape of the opening is a square having a side of 10 ⁇ m.
- the experimental data in which the distance between two adjacent coating regions is 0 ⁇ m, 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, and 450 ⁇ m are respectively 500 ⁇ m, 400 ⁇ m, and 300 ⁇ m. , 200 ⁇ m, 100 ⁇ m and 50 ⁇ m.
- the film of the GaAs layer 124 is obtained for the cases where the length of one side of the coating region is 480 ⁇ m and 450 ⁇ m, respectively, by the same procedure as other experimental data. Obtained by measuring the thickness.
- FIG. 13 shows that the growth rate of the GaAs layer 124 is very stable when the distance is 20 ⁇ m as compared with the case where the distance between two adjacent coating regions is 0 ⁇ m. From the above results, it can be seen that the growth rate of the crystal growing inside the opening is stabilized when the two adjacent coating regions are slightly separated. Alternatively, it can be seen that the growth rate of the crystal is stabilized if a region where crystal growth occurs is arranged between two adjacent coating regions. In addition, even when the distance between two adjacent coating regions is 0 ⁇ m, it can be seen that the variation in the growth rate of the crystal can be suppressed by arranging a plurality of openings at equal intervals.
- Example 2 The length of one side of the covering region is set to 200 ⁇ m, 500 ⁇ m, 700 ⁇ m, 1000 ⁇ m, 1500 ⁇ m, 2000 ⁇ m, 3000 ⁇ m, or 4250 ⁇ m, and in each case, a semiconductor substrate is manufactured in the same procedure as in Example 1, The film thickness of the GaAs layer 124 formed inside the opening was measured.
- the SiO 2 layer was formed so that a plurality of SiO 2 layers having the same size were arranged on the Si wafer 102. Further, the SiO 2 layer was formed so that the plurality of SiO 2 layers were separated from each other.
- the bottom shape of the opening was tested in three ways: a square with a side of 10 ⁇ m, a square with a side of 20 ⁇ m, a rectangle with a short side of 30 ⁇ m and a long side of 40 ⁇ m.
- the growth conditions of the Ge layer 120 and the GaAs layer 124 were set to the same conditions as in Example 1.
- Example 3 The film thickness of the GaAs layer 124 formed inside the opening was measured in the same manner as in Example 2 except that the supply amount of trimethylgallium was halved and the growth rate of the GaAs layer 124 was halved.
- the length of one side of the covering region was set to 200 ⁇ m, 500 ⁇ m, 1000 ⁇ m, 2000 ⁇ m, 3000 ⁇ m, or 4250 ⁇ m, and the experiment was performed when the bottom shape of the opening was a square with a side of 10 ⁇ m.
- Example 2 and Example 3 The experimental results of Example 2 and Example 3 are shown in FIG. 14, FIG. 15 to FIG. 19, FIG. 20 to FIG. In FIG. 14, the average value of the film thickness of the GaAs layer 124 in each case of Example 2 is shown. 15 to 19 show electron micrographs of the GaAs layer 124 in each case of Example 2. FIG. 20 to 24 show electron micrographs of the GaAs layer 124 in each case of Example 3. FIG. Table 1 shows the growth rate of the GaAs layer 124 and the Ra value in each case of Example 2 and Example 3.
- FIG. 14 shows the relationship between the growth rate of the GaAs layer 124 and the size of the covering region and the size of the opening.
- the vertical axis represents the film thickness of the GaAs layer 124 grown during a certain time
- the horizontal axis represents the length [ ⁇ m] of one side of the covered region.
- an approximate value of the growth rate of the GaAs layer 124 can be obtained by dividing the film thickness by the time.
- the rhombus plot shows experimental data when the bottom shape of the opening is a square having a side of 10 ⁇ m
- the square plot shows experimental data when the bottom shape of the opening is a square having a side of 20 ⁇ m.
- a triangular plot shows experimental data when the bottom shape of the opening is a rectangle having a long side of 40 ⁇ m and a short side of 30 ⁇ m.
- FIG. 14 shows that the growth rate stably increases as the size of the covering region increases until the length of one side of the covering region reaches 4250 ⁇ m. From the result shown in FIG. 12 and the result shown in FIG. 14, it can be seen that the growth rate of the crystal growing inside the opening is stabilized when the two adjacent coating regions are slightly separated. Alternatively, it can be seen that the growth rate of the crystal is stabilized if a region where crystal growth occurs is arranged between two adjacent coating regions.
- FIGS. 15, 16, 17, 18, and 19 show the results when the length of one side of the covered region is 4250 ⁇ m, 2000 ⁇ m, 1000 ⁇ m, 500 ⁇ m, and 200 ⁇ m, respectively. 15 to 19, it can be seen that the surface state of the GaAs layer 124 deteriorates as the size of the covering region increases.
- FIG. 20 to 24 show the results of observing the surface of the GaAs layer 124 with an electron microscope in each case of Example 3.
- FIG. 20, FIG. 21, FIG. 22, FIG. 23, and FIG. 24 show the results when the length of one side of the covered region is 4250 ⁇ m, 2000 ⁇ m, 1000 ⁇ m, 500 ⁇ m, and 200 ⁇ m, respectively.
- 20 to 24 it can be seen that the surface state of the GaAs layer 124 deteriorates as the size of the covering region increases. Further, it can be seen that the surface state of the GaAs layer 124 is improved as compared with the result of Example 2.
- Table 1 shows the growth rate [ ⁇ / min] of the GaAs layer 124 and the Ra value [ ⁇ m] in each case of Example 2 and Example 3.
- the film thickness of the GaAs layer 124 was measured with a needle type step gauge.
- Ra value was computed based on the observation result by a laser microscope apparatus. From Table 1, it can be seen that the smaller the growth rate of the GaAs layer 124, the better the surface roughness. It can also be seen that the Ra value is 0.02 ⁇ m or less when the growth rate of the GaAs layer 124 is 300 nm / min or less.
- Example 4 In the same manner as in Example 1, a semiconductor substrate including the Si wafer 102, the insulating layer 104, the Ge layer 120, and the GaAs layer 124 was produced.
- the insulating layer 104 was formed on the (100) surface of the surface of the Si wafer 102. 25 to 27 show electron micrographs of the surface of the GaAs crystal formed on the semiconductor substrate.
- FIG. 25 shows a result when a GaAs crystal is grown in an opening arranged so that the direction of one side of the bottom shape of the opening and the ⁇ 010> direction of the Si wafer 102 are substantially parallel to each other.
- the planar shape of the covering region was a square having a side length of 300 ⁇ m.
- the bottom shape of the opening was a square having a side of 10 ⁇ m.
- the arrow in the figure indicates the ⁇ 010> direction.
- a crystal having a uniform shape was obtained.
- FIG. 25 shows that the (10-1) plane, the (1-10) plane, the (101) plane, and the (110) plane appear on the four side surfaces of the GaAs crystal, respectively.
- the (11-1) plane appears in the upper left corner of the GaAs crystal
- the (1-11) plane appears in the lower right corner of the GaAs crystal in the figure. Recognize.
- the (11-1) plane and the (1-11) plane are equivalent planes to the (-1-1-1) plane and are stable planes.
- FIG. 26 shows a result when a GaAs crystal is grown in an opening arranged so that the direction of one side of the bottom shape of the opening and the ⁇ 010> direction of the Si wafer 102 are substantially parallel to each other. .
- FIG. 26 shows the results when observed obliquely from above at an angle of 45 °.
- the planar shape of the covering region was a square having a side length of 50 ⁇ m.
- the bottom shape of the opening was a square having a side length of 10 ⁇ m.
- the arrow in the figure indicates the ⁇ 010> direction.
- a crystal having a uniform shape was obtained.
- FIG. 27 shows a result when a GaAs crystal is grown in an opening arranged so that the direction of one side of the bottom shape of the opening and the ⁇ 011> direction of the Si wafer 102 are substantially parallel to each other.
- the planar shape of the covering region was a square having a side length of 400 ⁇ m.
- the bottom shape of the opening was a square having a side length of 10 ⁇ m.
- the arrow in the figure indicates the ⁇ 011> direction.
- FIG. 27 compared with FIG. 25 and FIG. 26, a crystal with a disordered shape was obtained.
- As a result of the appearance of a relatively unstable (111) plane on the side surface of the GaAs crystal it is considered that the shape of the crystal is disturbed.
- Example 5 In the same manner as in Example 1, a semiconductor substrate including the Si wafer 102, the insulating layer 104, the Ge layer 120, and the GaAs layer 124 was produced. In this embodiment, an intermediate layer is formed between the Ge layer 120 and the GaAs layer 124.
- the planar shape of the covering region was a square having a side length of 200 ⁇ m.
- the bottom shape of the opening was a square having a side of 10 ⁇ m.
- a Ge layer 120 having a film thickness of 850 nm was formed inside the opening by a CVD method, and then annealed at 800 ° C.
- the temperature of the Si wafer 102 on which the Ge layer 120 was formed was set to 550 ° C., and an intermediate layer was formed by MOCVD.
- the intermediate layer was grown using trimethylgallium and arsine as source gases.
- the film thickness of the intermediate layer was 30 nm.
- the temperature of the Si wafer 102 on which the intermediate layer was formed was raised to 640 ° C., and then the GaAs layer 124 was formed by MOCVD.
- the thickness of the GaAs layer was 500 nm.
- a semiconductor substrate was fabricated under the same conditions as in Example 1.
- FIG. 28 shows the result of observing a cross section of the manufactured semiconductor substrate with a transmission electron microscope. As shown in FIG. 28, no dislocation was observed in the Ge layer 120 and the GaAs layer. Thus, it can be seen that, by adopting the above configuration, a high-quality Ge layer and a compound semiconductor layer lattice-matched or pseudo-lattice-matched to the Ge layer can be formed on the Si substrate.
- Example 6 In the same manner as in Example 5, a semiconductor substrate including the Si wafer 102, the insulating layer 104, the Ge layer 120, the intermediate layer, and the GaAs layer 124 was manufactured, and then the HBT was obtained using the obtained semiconductor substrate. An element structure was produced. The HBT element structure was fabricated by the following procedure. First, a semiconductor substrate was produced in the same manner as in Example 5. In the present example, the planar shape of the covering region was a square having a side length of 50 ⁇ m. The bottom shape of the opening was a square having a side of 20 ⁇ m. Regarding other conditions, the semiconductor substrate was formed under the same conditions as in Example 5.
- a semiconductor layer was stacked on the surface of the GaAs layer of the semiconductor substrate by MOCVD.
- an HBT element structure was obtained in which an n-type GaAs layer having a thickness of 120 nm and an n-type InGaAs layer having a thickness of 60 nm were arranged in this order
- An electrode was arranged on the obtained HBT element structure to produce an HBT element as an example of an electronic element or an electronic device.
- Si was used as an n-type impurity.
- C was used as a p-type impurity.
- FIG. 29 shows a laser microscope image of the obtained HBT element.
- the light gray portion indicates the electrode.
- three electrodes are lined up in the opening region arranged near the center of the square covering region.
- the three electrodes respectively indicate a base electrode, an emitter electrode, and a collector electrode of the HBT element from the left in the figure.
- transistor operation was confirmed. Further, when the cross section of the HBT element was observed with a transmission electron microscope, no dislocation was observed.
- Example 7 In the same manner as in Example 6, three HBT elements having the same structure as in Example 6 were produced. The three manufactured HBT elements were connected in parallel. In this example, the planar shape of the covering region was a rectangle having a long side of 100 ⁇ m and a short side of 50 ⁇ m. Moreover, three openings were provided inside the covering region. All of the bottom shapes of the openings were squares having a side of 15 ⁇ m. Regarding other conditions, an HBT element was manufactured under the same conditions as in Example 6.
- FIG. 30 shows a laser microscope image of the obtained HBT element.
- the light gray portion indicates the electrode.
- FIG. 30 shows that three HBT elements are connected in parallel.
- Example 8 An HBT element was manufactured by changing the bottom area of the opening, and the relationship between the bottom area of the opening and the electrical characteristics of the obtained HBT element was examined. An HBT element was fabricated in the same manner as in Example 6. As electrical characteristics of the HBT element, a base sheet resistance value R b [ ⁇ / ⁇ ] and a current amplification factor ⁇ were measured. The current amplification factor ⁇ was obtained by dividing the collector current value by the base current value.
- the shape of the bottom of the opening is a square with a side of 20 ⁇ m, a rectangle with a short side of 20 ⁇ m and a long side of 40 ⁇ m, a square with a side of 30 ⁇ m, a rectangle with a short side of 30 ⁇ m and a long side of 40 ⁇ m, or a short
- An HBT element was manufactured for each of the rectangles having a side of 20 ⁇ m and a long side of 80 ⁇ m.
- the bottom shape of the opening is a square
- one of two orthogonal sides of the bottom shape of the opening is parallel to the ⁇ 010> direction of the Si wafer 102, and the other is parallel to the ⁇ 001> direction of the Si wafer 102.
- An opening was formed so that When the bottom shape of the opening is rectangular, the long side of the bottom shape of the opening is parallel to the ⁇ 010> direction of the Si wafer 102, and the short side is parallel to the ⁇ 001> direction of the Si wafer 102.
- An opening was formed.
- the planar shape of the covering region was mainly tested in the case of a square having a side of 300 ⁇ m.
- FIG. 31 shows the relationship between the ratio of the current amplification factor ⁇ to the base sheet resistance value Rb of the HBT element and the bottom area [ ⁇ m 2 ] of the opening.
- the vertical axis indicates a value obtained by dividing the current amplification factor ⁇ by the base sheet resistance value Rb
- the horizontal axis indicates the bottom area of the opening.
- FIG. 31 does not show the value of the current amplification factor ⁇ , but a high value of about 70 to 100 was obtained for the current amplification factor.
- the current amplification factor ⁇ was 10 or less.
- the HBT element structure by forming the HBT element structure locally on the surface of the Si wafer 102, a device having excellent electrical characteristics can be manufactured.
- the length of one side of the bottom shape of the opening is 80 ⁇ m or less, or the bottom area of the opening is 1600 ⁇ m 2 or less, a device having excellent electrical characteristics can be manufactured.
- a step of forming an insulating layer on a single crystal Si substrate a step of patterning the insulating layer to form an opening in the insulating layer by exposing the substrate, and an insulating layer in which the opening is formed
- introducing a source gas into the CVD reaction chamber that can be brought into an ultra-high vacuum reduced pressure state, introducing the source gas into the CVD reaction chamber, and heating the substrate to a first temperature at which the source gas can be thermally decomposed, thereby opening the substrate.
- a semiconductor substrate could be produced by a method for producing a semiconductor substrate, comprising introducing a source gas capable of forming a GaAs layer into a CVD reaction chamber, and epitaxially growing the GaAs layer on the surface of the Ge layer whose surface has been treated.
- a crystal thin film having excellent crystallinity can be formed on an inexpensive silicon substrate, and a semiconductor substrate, an electronic device, or the like can be formed using the crystal thin film.
Abstract
Description
Hsin-Chiao Luan et.al.、「High-quality Ge epilayers on Si with low threading-dislocation densities」、APPLIED PHYSICS LETTERS、VOLUME 75, NUMBER 19、8 NOVEMBER 1999.
Siウェハ102と、絶縁層104と、Ge層120と、GaAs層124とを備えた半導体基板を作製して、絶縁層104に形成した開口の内部に成長する結晶の成長速度と、被覆領域の大きさおよび開口の大きさとの関係を調べた。実験は、絶縁層104に形成される被覆領域の平面形状および開口の底面形状を変えて、一定時間の間に成長するGaAs層124の膜厚を測定することで実施した。
被覆領域の一辺の長さを200μm、500μm、700μm、1000μm、1500μm、2000μm、3000μmまたは4250μmに設定して、それぞれの場合について、実施例1の場合と同様の手順で半導体基板を作製して、開口の内部に形成されたGaAs層124の膜厚を測定した。本実施例では、Siウェハ102の上に同一の大きさのSiO2層が複数配されるように、当該SiO2層を形成した。また、上記複数のSiO2層が互いに離間するよう、当該SiO2層を形成した。開口の底面形状は、実施例1と同様に、一辺が10μmの正方形の場合、一辺が20μmの正方形の場合、短辺が30μmで長辺が40μmの長方形である場合の3通りについて実験した。Ge層120およびGaAs層124の成長条件は実施例1と同一の条件に設定した。
トリメチルガリウムの供給量を半分にして、GaAs層124の成長速度を約半分にした以外は実施例2の場合と同様にして、開口の内部に形成されたGaAs層124の膜厚を測定した。なお、実施例3では、被覆領域の一辺の長さを200μm、500μm、1000μm、2000μm、3000μmまたは4250μmに設定して、開口の底面形状が一辺が10μmの正方形の場合について、実験を実施した。
実施例1と同様にして、Siウェハ102と、絶縁層104と、Ge層120と、GaAs層124とを備えた半導体基板を作製した。本実施例では、Siウェハ102の表面の(100)面に絶縁層104を形成した。図25から図27に、上記半導体基板に形成されたGaAs結晶の表面の電子顕微鏡写真を示す。
実施例1と同様にして、Siウェハ102と、絶縁層104と、Ge層120と、GaAs層124とを備えた半導体基板を作製した。本実施例においては、Ge層120と、GaAs層124との間に中間層を形成した。本実施例において、被覆領域の平面形状は、一辺の長さが200μmの正方形であった。開口の底面形状は、一辺が10μmの正方形であった。CVD法により、開口の内部に、膜厚が850nmのGe層120を形成した後、800℃でアニール処理を実施した。
実施例5と同様にして、Siウェハ102と、絶縁層104と、Ge層120と、中間層と、GaAs層124とを備えた半導体基板を作製した後、得られた半導体基板を用いてHBT素子構造を作製した。HBT素子構造は、以下の手順で作製した。まず、実施例5の場合と同様にして、半導体基板を作製した。なお、本実施例では、被覆領域の平面形状は、一辺の長さが50μmの正方形であった。開口の底面形状は、一辺が20μmの正方形であった。それ以外の条件については、実施例5の場合と同一の条件で半導体基板をした。
実施例6と同様にして、実施例6と同様の構造を有するHBT素子を3つ作製した。作製した3つのHBT素子を並列接続した。本実施例では、被覆領域の平面形状は、長辺が100μm、短辺が50μmの長方形であった。また、上記被覆領域の内部に、3つの開口を設けた。開口の底面形状は、すべて、一辺が15μmの正方形であった。それ以外の条件については、実施例6の場合と同一の条件でHBT素子を作製した。
開口の底面積を変えてHBT素子を作製して、開口の底面積と、得られたHBT素子の電気特性との関係を調べた。実施例6と同様にして、HBT素子を作製した。HBT素子の電気特性として、ベースシート抵抗値Rb[Ω/□]および電流増幅率βを測定した。電流増幅率βは、コレクタ電流の値をベース電流の値で除して求めた。本実施例では、開口の底面形状が、一辺が20μmの正方形、短辺が20μmで長辺が40μmの長方形、一辺が30μmの正方形、短辺が30μmで長辺が40μmの長方形、または、短辺が20μmで長辺が80μmの長方形の場合のそれぞれについて、HBT素子を作製した。
Claims (32)
- 単結晶Siの基板と、
前記基板の上に形成され、開口領域を有する絶縁層と、
前記開口領域の前記基板上にエピタキシャル成長されたGe層と、
前記Ge層の上にエピタキシャル成長されたGaAs層と、
を備え、
前記Ge層は、超高真空の減圧状態にできるCVD反応室に前記基板を導入し、原料ガスを熱分解できる第1温度で第1のエピタキシャル成長を実施し、前記第1温度より高い第2温度で第2のエピタキシャル成長を実施し、前記第1および第2のエピタキシャル成長を実施したエピタキシャル層をGeの融点に達しない第3温度で第1のアニールを実施し、前記第3温度より低い第4温度で第2のアニールを実施して形成された半導体基板。 - 前記Ge層は、前記第1のアニールおよび前記第2のアニールを複数回繰り返して形成する、
請求項1に記載の半導体基板。 - 前記絶縁層は、酸化シリコン層である、
請求項1または請求項2に記載の半導体基板。 - 単結晶Siの基板と、
前記基板の主面に対し略垂直な方向に貫通して前記基板を露出させてなる開口が形成された絶縁層と、
前記開口の内部の前記基板の上に結晶成長されたGe層と、
前記Ge層の上にエピタキシャル成長されたGaAs層と、
を含み、
前記Ge層は、超高真空の減圧状態にできるCVD反応室に前記基板を導入し、原料ガスを熱分解できる第1温度で第1のエピタキシャル成長を実施し、前記第1温度より高い第2温度で第2のエピタキシャル成長を実施し、前記第1および第2のエピタキシャル成長を実施したエピタキシャル層をGeの融点に達しない第3温度で第1のアニールを実施し、前記第3温度より低い第4温度で第2のアニールを実施して形成された半導体基板。 - 前記Ge層は、前記第1のアニールおよび前記第2のアニールから選択された1以上のアニールが、水素を含む雰囲気中で実施されて形成された、
請求項4に記載の半導体基板。 - 前記Ge層は、ハロゲン元素を含むガスを原料ガスに含むCVD法を用いて、前記開口に選択的に結晶成長されて形成された、
請求項4または請求項5に記載の半導体基板。 - 前記GaAs層の算術平均粗さは、0.02μm以下である、
請求項4から請求項6までの何れか一項に記載の半導体基板。 - 前記絶縁層は、酸化シリコン層である、
請求項4から請求項7までの何れか一項に記載の半導体基板。 - 前記絶縁層は、前記開口を複数有し、
前記複数の開口のうち一の開口と、前記一の開口に隣接する他の開口との間に、前記絶縁層の上面よりも高い吸着速度で前記GaAs層の原料を吸着する原料吸着部を含む、
請求項4から請求項8までの何れか一項に記載の半導体基板。 - 前記絶縁層を複数有し、
前記複数の絶縁層のうち一の絶縁層と、前記一の絶縁層に隣接する他の絶縁層との間に、前記複数の絶縁層の何れの上面よりも高い吸着速度で前記GaAs層の原料を吸着する原料吸着部を含む、
請求項4から請求項9までの何れか一項に記載の半導体基板。 - 前記原料吸着部は、前記基板に達する溝である、
請求項9または請求項10に記載の半導体基板。 - 前記溝の幅は、20μm以上、500μm以下である、
請求項11に記載の半導体基板。 - 前記原料吸着部を複数有し、
前記複数の原料吸着部の各々は、等間隔に配置されている、
請求項9から請求項12までの何れか一項に記載の半導体基板。 - 前記開口の底面積は、1mm2以下である、
請求項4から請求項13までの何れか一項に記載の半導体基板。 - 前記開口の底面積は、1600μm2以下である、
請求項14に記載の半導体基板。 - 前記開口の底面積は、900μm2以下である、
請求項15に記載の半導体基板。 - 前記開口の底面は、長方形であり、
前記長方形の長辺は、80μm以下である、
請求項14に記載の半導体基板。 - 前記開口の底面は、長方形であり、
前記長方形の長辺は、40μm以下である、
請求項15に記載の半導体基板。 - 前記基板の主面が(100)面であり、
前記開口の底面は、正方形または長方形であり、
前記正方形または前記長方形の少なくとも1辺の方向は、前記主面における<010>方向、<0-10>方向、<001>方向および<00-1>方向からなる群から選択された何れか一つの方向と実質的に平行である、
請求項4から請求項18までの何れか一項に記載の半導体基板。 - 前記基板の主面が(111)面であり、
前記開口の底面は、六角形であり、
前記六角形の少なくとも1辺の方向は、前記主面における<1-10>方向、<-110>方向、<0-11>方向、<01-1>方向、<10-1>方向および<-101>方向からなる群から選択された何れか一つの方向と実質的に平行である、
請求項4から請求項18までの何れか一項に記載の半導体基板。 - 単結晶Siの基板の上に絶縁層を形成する段階と、
前記絶縁層をパターニングして、前記絶縁層に前記基板を露出する開口領域を形成する段階と、
前記開口領域を有する前記絶縁層が形成された前記基板を、超高真空の減圧状態にできるCVD反応室に導入する段階と、
前記CVD反応室に原料ガスを導入するとともに、前記原料ガスを熱分解できる第1温度に前記基板を加熱して、前記開口領域に露出された前記基板にGeの第1エピタキシャル層を選択的に形成する段階と、
前記CVD反応室に原料ガスを導入するとともに、前記第1温度より高い第2温度に前記基板を加熱して、前記第1エピタキシャル層の上にGeの第2エピタキシャル層を形成する段階と、
前記第1および第2エピタキシャル層に、Geの融点に達しない第3温度でアニールを施す段階と、
前記第1および第2エピタキシャル層に、第3温度より低い第4温度でアニールを施す段階と、
アニールを施した後のGe層の表面にフォスフィンを含むガスを供給して、前記Ge層の表面を処理する段階と、
前記CVD反応室にGaAs層を形成し得る原料ガスを導入して、前記表面が処理されたGe層に接して、GaAs層をエピタキシャル成長する段階と、
を備える半導体基板の製造方法。 - 前記第3温度でのアニールを施す段階と前記第4温度でアニールを施す段階とを複数回繰り返す段階、
をさらに備える請求項21に記載の半導体基板の製造方法。 - 前記絶縁層は、酸化シリコン層である、
請求項21または請求項22に記載の半導体基板の製造方法。 - 単結晶Siの基板の上に絶縁層を形成する段階と、
前記絶縁層をパターニングして、前記基板を露出させてなる開口を前記絶縁層に形成する段階と、
前記開口が形成された前記絶縁層を含む前記基板を、超高真空の減圧状態にできるCVD反応室に導入する段階と、
前記CVD反応室に原料ガスを導入するとともに、前記原料ガスを熱分解できる第1温度に前記基板を加熱して、前記開口に露出された前記基板にGeの第1エピタキシャル層を選択的に形成する段階と、
前記CVD反応室に原料ガスを導入するとともに、前記第1温度より高い第2温度に前記基板を加熱して、前記第1エピタキシャル層の上にGeの第2エピタキシャル層を形成する段階と、
前記第1エピタキシャル層および前記第2エピタキシャル層に、Geの融点に達しない第3温度でアニールする段階と、
前記第1エピタキシャル層および前記第2エピタキシャル層に、第3温度より低い第4温度でアニールする段階と、
アニールを施した後のGe層の表面にフォスフィンを含むガスを供給し、前記Ge層の表面を処理する段階と、
前記CVD反応室にGaAs層を形成し得る原料ガスを導入し、前記表面が処理されたGe層の表面に、GaAs層をエピタキシャル成長させる段階と、
を含む半導体基板の製造方法。 - 前記第3温度および前記第4温度の少なくとも1つの温度は、680℃以上900℃未満である、
請求項24に記載の半導体基板の製造方法。 - 前記第3温度でアニールする段階は、前記Ge層を、水素を含む雰囲気中でアニールする、
請求項24または請求項25に記載の半導体基板の製造方法。 - 前記第4温度でアニールする段階は、前記Ge層を、水素を含む雰囲気中でアニールする、
請求項24から請求項26までの何れか一項に記載の半導体基板の製造方法。 - 前記Geの第1エピタキシャル層を選択的に形成する段階は、前記Ge層を、0.1Pa以上100Pa以下の圧力下でCVD法により、前記開口に選択的に結晶成長させる、
請求項24から請求項27までの何れか一項に記載の半導体基板の製造方法。 - 前記Geの第2エピタキシャル層を選択的に形成する段階は、前記Ge層を、0.1Pa以上100Pa以下の圧力下でCVD法により、前記開口に選択的に結晶成長させる、
請求項24から請求項28までの何れか一項に記載の半導体基板の製造方法。 - 前記Geの第1エピタキシャル層を選択的に形成する段階は、前記Ge層を、ハロゲン元素を含むガスを原料ガスに含む雰囲気中でCVD法により、前記開口に選択的に結晶成長させる、
請求項24から請求項29までの何れか一項に記載の半導体基板の製造方法。 - 前記Geの第2エピタキシャル層を選択的に形成する段階は、前記Ge層を、ハロゲン元素を含むガスを原料ガスに含む雰囲気中でCVD法により、前記開口に選択的に結晶成長させる、
請求項24から請求項30までの何れか一項に記載の半導体基板の製造方法。 - 前記GaAs層をエピタキシャル成長させる段階は、前記GaAs層を、1nm/min以上、300nm/min以下の成長速度で結晶成長させる、
請求項24から請求項31までの何れか一項に記載の半導体基板の製造方法。
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TW201025426A (en) * | 2008-10-02 | 2010-07-01 | Sumitomo Chemical Co | Semiconductor wafer, electronic device and method for making a semiconductor wafer |
TWI471910B (zh) | 2008-10-02 | 2015-02-01 | Sumitomo Chemical Co | 半導體晶圓、電子裝置及半導體晶圓之製造方法 |
US20110227199A1 (en) * | 2008-11-28 | 2011-09-22 | Sumitomo Chemical Company, Limited | Method for producing semiconductor substrate, semiconductor substrate, method for manufacturing electronic device, and reaction apparatus |
CN102227802A (zh) * | 2008-11-28 | 2011-10-26 | 住友化学株式会社 | 半导体基板的制造方法、半导体基板、电子器件的制造方法、和反应装置 |
CN102341889A (zh) | 2009-03-11 | 2012-02-01 | 住友化学株式会社 | 半导体基板、半导体基板的制造方法、电子器件、和电子器件的制造方法 |
KR20120022872A (ko) | 2009-05-22 | 2012-03-12 | 스미또모 가가꾸 가부시키가이샤 | 반도체 기판, 전자 디바이스, 반도체 기판의 제조 방법 및 전자 디바이스의 제조 방법 |
WO2010140370A1 (ja) | 2009-06-05 | 2010-12-09 | 住友化学株式会社 | 光デバイス、半導体基板、光デバイスの製造方法、および半導体基板の製造方法 |
KR101671552B1 (ko) | 2009-06-05 | 2016-11-01 | 내셔날 인스티튜트 오브 어드밴스드 인더스트리얼 사이언스 앤드 테크놀로지 | 센서, 반도체 기판 및 반도체 기판의 제조 방법 |
CN102449775B (zh) | 2009-06-05 | 2014-07-02 | 独立行政法人产业技术综合研究所 | 半导体基板、光电转换器件、半导体基板的制造方法和光电转换器件的制造方法 |
JP2011114160A (ja) * | 2009-11-26 | 2011-06-09 | Sumitomo Chemical Co Ltd | 半導体基板、電子デバイスおよび半導体基板の製造方法 |
JP5667360B2 (ja) * | 2009-12-21 | 2015-02-12 | 住友化学株式会社 | 半導体基板、電子デバイスおよび半導体基板の製造方法 |
JP2011204720A (ja) * | 2010-03-24 | 2011-10-13 | Toshiba Corp | 半導体装置の製造方法 |
JP5943645B2 (ja) | 2011-03-07 | 2016-07-05 | 住友化学株式会社 | 半導体基板、半導体装置および半導体基板の製造方法 |
TWI458090B (zh) * | 2011-12-22 | 2014-10-21 | Nat Inst Chung Shan Science & Technology | Structure and method for manufacturing a crystalline layer on a patterned insulating layer |
TWI505331B (zh) * | 2012-06-19 | 2015-10-21 | Hermes Epitek Corp | 磊晶成長製程及結構 |
WO2014050187A1 (ja) * | 2012-09-28 | 2014-04-03 | 独立行政法人科学技術振興機構 | ゲルマニウム層の表面の平坦化方法並びに半導体構造およびその製造方法 |
US10879124B2 (en) * | 2017-11-21 | 2020-12-29 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method to form a fully strained channel region |
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JP2009177169A (ja) | 2009-08-06 |
TW200941559A (en) | 2009-10-01 |
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