Crystal film, laminated structure, semiconductor device, electronic device, and system

Abstract

[Problem] To provide: a crystal film excellent in crystallinity and useful for a semiconductor device and the like; and a laminated structure. [Solution] This crystal film comprises an oxide compound including germanium as a main component, wherein the oxide compound further includes at least one metal element of group 4 of the periodic table. The crystal film having tetragonal crystal structure, an area of 100 mm2 or more, and a thickness of 1 μm or more is used and applied to, for example, a semiconductor device.

Description

Crystalline film, laminated structure, semiconductor device, electronic device and system

[0001] The present invention relates to a crystalline film and a laminated structure useful for semiconductor devices.

[0002] Conventionally, Ga ２ O ３ is attracting attention as a promising ultra-wide bandgap (UWBG) semiconductor for future power electronics devices.

[0003] However, Ga ２ O ３ However, there are problems with the difficulty of producing p-type semiconductors, and it is not easy to make them inexpensive, so there are still many issues to be overcome before they can be widely used. In recent years, rutile germanium dioxide (r-GeO) has been developed as a new UWBG semiconductor (band gap 4.44-4.68 eV). ２ ) has been studied, and rutile germanium dioxide can be used as n-type and p-type semiconductors and can be produced inexpensively, so Ga ２ O ３ It is expected to be a UWBG semiconductor to replace r-TiO ２ r-GeO on (001) substrate ２ Laminated structures in which crystalline films are stacked have been studied (Non-Patent Document 1, Patent Document 1, Patent Document 2, and Patent Document 3). However, Non-Patent Document 2 was submitted as an erratum after the peer review of Non-Patent Document 1 (Non-Patent Document 2). It was found that the crystal grains (abnormal grains) described in Non-Patent Document 1, Patent Document 1, Patent Document 2, and Patent Document 3 were rutile-type germanium dioxide crystals, and the remaining portions were amorphous phases. In other words, only amorphous phases were formed in the majority of the structure, and even if a crystalline phase was formed, crystal grains were only formed in a portion of the structure. Therefore, a method for producing a crystalline film with excellent electrical control has been eagerly awaited.

[0004] Takane, K. Kaneko, “Establishment of a growth route of crystallized rutile GeO2 thin film (≧ 1 mm / h) and its structural “Applied Physics Letters Vol. 119, pp. 062104(1-6) (2021). Takane, K. Kaneko, Erratum: “Establishment of a growth route of crystallized rutile GeO2 thin film (≧1 μm / h) and its “structural properties” Applied Physics Letters Vol. 120, 099903(1-3) (2022).

[0005] International Publication No. 2023 / 008454 International Publication No. 2023 / 008453 International Publication No. 2023 / 008452

[0006] An object of the present invention is to provide a crystalline film and a layered structure having excellent crystallinity that are useful for semiconductor devices and the like.

[0007] As a result of intensive research to achieve the above object, the present inventors newly developed a mist CVD apparatus using a guide partition, and by using the mist CVD apparatus using the guide partition, they succeeded in creating a crystalline film containing a compound oxide containing germanium as a main component, wherein the compound oxide further contains at least one metal element of Group 4 of the periodic table, and found that the obtained crystal has excellent crystallinity and is useful for semiconductor devices, etc., and discovered that such a crystal can solve all of the above-mentioned conventional problems at once. Furthermore, after obtaining the above findings, the present inventors further conducted research and completed the present invention.

[0008] That is, the present invention relates to the following inventions. [1] A crystalline film containing a compound containing germanium as a main component, characterized in that the compound oxide further contains at least one metal element of Group 4 of the periodic table. [2] The crystalline film according to [1] above, which has a tetragonal crystal structure. [3] 100 mm ２[4] The crystal film according to [1], having an area of ​​1 μm or more. [5] The crystal film according to [1], having a film thickness of 1 μm or more. [6] The crystal film according to [1], being single crystal. [7] The crystal film according to [1], wherein the compound oxide contains titanium. [8] The crystal film according to [1], having an electrical resistivity of 10 Ωcm or less. [9] The crystal film according to [1], which is a p-type semiconductor.

[10] The crystal film according to [1], which forms an ohmic contact with a metal layer.

[11] A crystal mainly composed of an oxide semiconductor having a rutile structure, wherein the oxide semiconductor contains germanium and is a p-type semiconductor.

[12] The crystal according to

[11] , which is in the form of a film.

[13] A layered structure in which a crystal film is layered on a crystal substrate directly or via another layer, wherein the crystal film is the crystal film according to [1] or the crystal according to

[12] .

[14] A laminated structure in which an ohmic contact is formed between a metal layer and a crystalline film, wherein the crystalline film is the crystalline film described in [1] above or the crystal described in

[12] above.

[15] The laminated structure described in

[13] above, wherein the metal layer contains one or more metal elements selected from d-block metal elements and / or p-block metal elements of the periodic table.

[16] The laminated structure described in

[15] above, wherein the metal layer contains indium.

[17] A semiconductor device including a crystalline film or laminated structure, wherein the crystalline film is the crystalline film described in [1] above or the crystal described in

[12] above, and the laminated structure is the laminated structure described in

[13] or

[14] above.

[18] The semiconductor device described in

[17] above, which is a power device.

[19] The semiconductor device according to

[17] , which is a Schottky barrier diode (SBD), a junction barrier Schottky diode (JBS), a high electron mobility transistor (HEMT), a metal oxide semiconductor field effect transistor (MOSFET), a junction field effect transistor (JFET), an insulated gate bipolar transistor (IGBT), or a light emitting diode (LED).

[20] An electronic device including a semiconductor device, wherein the semiconductor device is the semiconductor device described in

[17] .

[21] A system including an electronic device, wherein the electronic device is the electronic device described in

[20] .

[0009] The crystalline film and laminated structure of the present invention are useful for semiconductor devices and the like, and exhibit excellent crystallinity.

[0010] 7 is a schematic diagram of a film formation apparatus (mist CVD) preferably used in the present invention. FIG. 8 is a diagram schematically showing an atomization apparatus preferably used in the present invention. FIG. 9 is a diagram showing XRD diffraction results in Example 1. FIG. 10 is a diagram showing an SEM image in Example 1. FIG. 11 is a diagram showing an EDS image in Example 1. FIG. 12 is a diagram showing an AFM image in Example 1. FIG. 13 is a diagram showing a sample in which an ohmic electrode is formed on a crystalline film in Example 1. FIG. 14 is a diagram showing the results of ohmic measurement using the sample of FIG. 7. FIG. 15 is a diagram showing a preferred example of a Schottky barrier diode (SBD) of the present invention. FIG. 16 is a diagram showing a preferred example of a high electron mobility transistor (HEMT) of the present invention. FIG. 17 is a diagram showing a preferred example of a metal oxide semiconductor field effect transistor (MOSFET) of the present invention. FIG. 18 is a diagram showing a preferred example of a junction field effect transistor (JFET) of the present invention. FIG. 19 is a diagram showing a preferred example of an insulated gate bipolar transistor (IGBT) of the present invention. FIG. 19 is a diagram showing a preferred example of a light emitting element (LED) of the present invention. 1 is a diagram showing a preferred example of a junction barrier Schottky diode (JBS) according to the present invention, and FIG. 2 is a diagram showing a cross-sectional side view of an atomization device preferably used in the present invention.

[0011] The crystal film of the present invention is a crystal film containing a germanium-containing compound as a main component, characterized in that the compound oxide further contains at least one metal element from Group 4 of the periodic table. The compound is preferably an oxide, but is not particularly limited as long as it does not impede the object of the present invention, and may be a nitride, carbide, or sulfide. The crystal film of the present invention preferably has a tetragonal crystal structure. According to such a preferred range, the interface can be made better and the semiconductor properties can also be made more excellent. Furthermore, in the present invention, the crystal film is preferably a film having a thickness of 100 mm. ２ It is preferable that the crystal film has an area of ​​1 μm or more, and is preferably single crystal. According to such a preferred range, semiconductor devices can be manufactured with greater industrial advantages. Furthermore, it is preferable that the film thickness of the crystal film is 1 μm or more, and the surface roughness of the crystal film is preferably 10 nm or less. According to such a preferred range, the semiconductor film can have better breakdown voltage. Furthermore, in the present invention, it is preferable that the compound oxide contains titanium. According to such a preferred range, it can have better crystallinity. Furthermore, in the present invention, it is preferable that the crystal film has an electrical resistivity of 10 Ωcm or less, and is preferably a p-type semiconductor. Furthermore, in the present invention, it is preferable that an ohmic contact is formed with the metal layer. According to such a preferred range, it can have better electrical properties. In the present invention, the electrical resistivity is measured using a four-probe measuring device in accordance with the four-probe method (JIS H 0602: Resistivity measurement method for silicon single crystals and silicon wafers by the four-probe method).

[0012] The crystal of the present invention is a crystal mainly composed of an oxide semiconductor having a rutile structure, characterized in that the oxide semiconductor contains germanium and is a p-type semiconductor. ２ It is preferable that the crystal has an area of ​​1000 nm or more, and that the crystal is in the form of a film. It is also preferable that the crystal is a single crystal film. Within such a preferable range, the semiconductor characteristics can be improved.

[0013] The laminate structure of the present invention is characterized in that the crystalline film is laminated on a crystalline substrate directly or via another layer. In this specification, "film" can be interpreted as "layer." A "laminated structure" refers to a structure including one or more crystalline layers, and may also include a layer other than a crystalline layer (e.g., an amorphous layer). The crystalline layer is preferably a single crystalline layer, but may also be a polycrystalline layer. Another feature of the present invention is a laminate structure in which an ohmic contact is formed between a metal layer and a crystal, and the crystal is the crystalline layer. The metal layer preferably contains one or more metal elements selected from d-block metal elements and / or p-block metal elements of the periodic table. Examples of the d-block metal elements include Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Pt, Au, Hg, Zn, Cd, and Pd. Examples of the p-block metal element include Al, Ga, In, Sn, Pb, Tl, Bi, and Po. In the present invention, the metal layer preferably contains indium. Within this preferred range, the ohmic characteristics can be improved.

[0014] The crystals are formed by using, for example, the film-forming apparatus shown in FIG. ２ Crystal films and mixed crystal films thereof can be more easily obtained by film formation. Furthermore, doping can be performed appropriately using the film formation apparatus. The doped crystals can be suitably used as semiconductor films or semiconductor layers, and n-type or p-type dopants can be applied using conventional doping methods for oxide semiconductors. Examples of n-type dopants include antimony (Sb), arsenic (As), bismuth (Bi), fluorine (F), niobium (Nb), vanadium (V), tantalum (Ta), and tungsten (W). Examples of p-type dopants include aluminum (Al), gallium (Ga), and indium (In). The present invention also encompasses stacked structures obtained in this manner.

[0015] Furthermore, the crystal substrate is not particularly limited as long as it does not impede the objectives of the present invention, and may be a known substrate, such as an insulating substrate, a conductive substrate, or a semiconductor substrate. It may be a single crystal substrate or a polycrystalline substrate. The crystal substrate may be a substrate having a metal film on its surface. When the crystal substrate is a conductive substrate, a vertical device can be fabricated without removing the substrate. The crystal structure of the crystal substrate is also not particularly limited as long as it does not impede the objectives of the present invention, and may be a known crystal substrate. Examples of the crystal structure of the crystal substrate include a hexagonal crystal structure, a cubic crystal structure, and a tetragonal crystal structure. Examples of crystal substrates having a hexagonal crystal structure include a GaN substrate, a SiC substrate, and a sapphire substrate (e.g., a-plane sapphire, m-plane sapphire, c-plane sapphire substrate, and r-plane sapphire substrate). Examples of crystal substrates having a tetragonal crystal structure include GeO ２ Substrate, SrTiO ３ Substrate, TiO ２ Substrate or MgF ２ Examples of the crystalline substrate having a cubic crystal structure include a Si substrate and a SiC substrate. The crystalline substrate may have an off-angle, specifically, an off-angle of 0.1° to 10°, for example.

[0016] The crystal film or the laminated structure can be used as is or after known processing such as substrate peeling, using known means, for example, in semiconductor devices. Examples of such semiconductor devices include Schottky barrier diodes (SBDs), junction barrier Schottky diodes (JBSs), high electron mobility transistors (HEMTs), metal oxide semiconductor field effect transistors (MOSFETs), junction field effect transistors (JFETs), insulated gate bipolar transistors (IGBTs), and light-emitting diodes (LEDs). These semiconductor devices can also be used in modules incorporating these semiconductor devices, electronic devices incorporating these semiconductor devices, and their components. These devices are useful for a variety of applications, particularly power devices. Semiconductor devices can be classified into horizontal devices (horizontal devices) in which an electrode is formed on one side of a semiconductor layer, and vertical devices (vertical devices) in which electrodes are formed on both the front and back sides of a semiconductor layer. In the present invention, the semiconductor device can be used in both horizontal and vertical devices.

[0017] Examples of semiconductor devices suitable for use in the present invention will be described in more detail below with reference to the drawings, but the present invention is not limited to these examples. Preferred examples in which the crystalline film or the crystalline layer in the laminate structure containing a compound oxide containing germanium as a main component are used as the semiconductor layer are shown below.

[0018] 9 shows a preferred example of a Schottky barrier diode (SBD) including an n-type semiconductor layer 101a, an n+ type semiconductor layer 101b, a p-type semiconductor layer 102, a metal layer 103, an insulator layer 104, a Schottky electrode 105a, and an ohmic electrode 105b. The metal layer 103 is made of a metal such as Al, and covers the Schottky electrode 105a.

[0019] FIG. 10 shows a preferred example of a high electron mobility transistor (HEMT) including an n-type semiconductor layer 121 a having a wide band gap, an n-type semiconductor layer 121 b having a narrow band gap, an n+ type semiconductor layer 121 c, a p-type semiconductor layer 123, a gate electrode 125 a, a source electrode 125 b, a drain electrode 125 c, and a substrate 129.

[0020] 11 shows a preferred example of a metal oxide semiconductor field effect transistor (MOSFET) including an n-type semiconductor layer 131a, a first n+ type semiconductor layer 131b, a second n+ type semiconductor layer 131c, a p-type semiconductor layer 132, a p+ type semiconductor layer 132a, a gate insulating film 134, a gate electrode 135a, a source electrode 135b, and a drain electrode 135c. Note that the p+ type semiconductor layer 132a may be a p-type semiconductor layer or may be the same as the p-type semiconductor layer 132.

[0021] FIG. 12 shows a preferred example of a junction field effect transistor (JFET) including an n-type semiconductor layer 141a, a first n+ type semiconductor layer 141b, a second n+ type semiconductor layer 141c, a p-type semiconductor layer 142, a gate electrode 145a, a source electrode 145b, and a drain electrode 145c.

[0022] FIG. 13 shows a preferred example of an insulated gate bipolar transistor (IGBT) including an n-type semiconductor layer 151, an n-type semiconductor layer 151a, an n+ type semiconductor layer 151b, a p-type semiconductor layer 152, a gate insulating film 154, a gate electrode 155a, an emitter electrode 155b, and a collector electrode 155c.

[0023] (LED) An example of a case where the semiconductor device of the present invention is a light-emitting diode (LED) is shown in Figure 14. The semiconductor light-emitting device of Figure 14 has an n-type semiconductor layer 161 on a second electrode 165b, and a light-emitting layer 163 is laminated on the n-type semiconductor layer 161. A p-type semiconductor layer 162 is laminated on the light-emitting layer 163. A translucent electrode 167 that transmits light generated by the light-emitting layer 163 is provided on the p-type semiconductor layer 162, and a first electrode 165a is laminated on the translucent electrode 167. The semiconductor light-emitting device of Figure 14 may be covered with a protective layer except for the electrode portion.

[0024] Examples of materials for the translucent electrode include conductive oxide materials containing indium (In) or titanium (Ti). ２ O ３ , ZnO, SnO ２ , Ga ２ O ３ , TiO２ , CeO ２ Alternatively, a mixed crystal of two or more of these materials or a doped material thereof may be used. A translucent electrode can be formed by applying these materials by a known method such as sputtering. After the formation of the translucent electrode, thermal annealing may be performed to make the translucent electrode transparent.

[0025] In the semiconductor light-emitting element of FIG. 14, the first electrode 165a is a positive electrode and the second electrode 165b is a negative electrode, and current is passed through these electrodes to the p-type semiconductor layer 162, the light-emitting layer 163, and the n-type semiconductor layer 161, causing the light-emitting layer 163 to emit light.

[0026] Examples of materials for the first electrode 165a and the second electrode 165b include metals such as Al, Mo, Co, Zr, Sn, Nb, Fe, Cr, Ta, Ti, Au, Pt, V, Mn, Ni, Cu, Hf, W, Ir, Zn, In, Pd, Nd, and Ag, or alloys thereof; conductive metal oxide films such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); organic conductive compounds such as polyaniline, polythiophene, and polypyrrole; and mixtures thereof. The method for forming the electrodes is not particularly limited, and they can be formed on the substrate according to a method appropriately selected from wet methods such as printing, spraying, and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD, taking into consideration their suitability for the material.

[0027] FIG. 15 shows the main components of a junction barrier Schottky diode (JBS) according to a preferred embodiment of the present invention. The JBS shown in FIG. 15 includes an ohmic electrode 1020, an n-type semiconductor layer 1010a, an n+-type semiconductor layer 1010b, a Schottky electrode 1030, and an electric field buffer region 1060. The Schottky electrode 1030 is composed of metal layers 1030a, 1030b, and 1030c. In the semiconductor device shown in FIG. 15, the outer ends of metal layers 1030a and / or 1030b serving as second electrode layers are located outside the outer end of metal layer 1030c serving as a first electrode layer. In the semiconductor device shown in FIG. 15, the electric field buffer region 1060 includes at least two electric field buffer regions 1060 in a plane including at least a portion of the second electrode layer located outside the outer end of the first electrode layer and the outer end of the second electrode. In the semiconductor device of FIG. 15, the electric field relaxation region 1060 is made of a p-type semiconductor, and forms a PN junction with the n-type semiconductor layer 1010a.

[0028] 15 may be formed by any known method without particular limitation, as long as it does not impede the object of the present invention, such as forming a film by vacuum deposition, CVD, sputtering, or various coating techniques, followed by patterning by photolithography, or directly patterning by printing or the like.

[0029] Example 1 Figure 1 is a diagram showing an example of a preferred embodiment of a film production apparatus when the atomization device of the present invention is used as a film production atomization table. The film production apparatus 19 is composed of a film-forming sample 20, a sample stage 21, a carrier gas source 22a, a carrier gas source 22b, a flow rate control valve 23a, a flow rate control valve 23b, a film production chamber 27, a heater 28, and an atomization device 30. The atomization device 30 is composed of a raw material partition 24, a raw material liquid to be atomized 24a, an ultrasonically transparent substrate 24b, a stage 24c, an ultrasonic vibrator 26, a guide partition 31, an ultrasonic transmission liquid tank 35, and an ultrasonic transmission liquid 36. Figure 2 is a diagram showing another preferred embodiment of a film production apparatus when the atomization device of the present invention is used as a film production atomization table. The atomization device 30 is composed of a raw material partition wall 24, a liquid material for atomization 24a, an ultrasonically transparent substrate 24b, a base 24c, an ultrasonic vibrator 26, a guide partition wall 31, an ultrasonic transmission liquid tank 35, and an ultrasonic transmission liquid 36. The sample stage 21 is made of quartz, and the surface on which the film-forming sample 20 is placed is inclined from the horizontal. By fabricating both the film-forming chamber 27 and the sample stage 21 from quartz, impurities originating from the device are prevented from being mixed into the crystalline film formed on the film-forming sample 20. The liquid material for atomization 24a is contained in the mist generating source 24. The guide partition wall 31 is in contact with the ultrasonically transparent substrate 38. Figure 16 is a schematic cross-sectional side view of the atomization device used in the present invention. The atomization device 30 in Figure 16 is composed of a raw material partition wall 24, an ultrasonically transparent substrate 24b, a base 24c, an ultrasonic vibrator 26, a guide partition wall 31, and an ultrasonic transmission liquid tank 35. The guide partition 31 is in contact with the ultrasonic wave transmission liquid tank 35. By using the guide partition 31, the ultrasonic waves generated by the ultrasonic vibrator 26 are transmitted to the raw material partition 24 more efficiently.

[0030] Next, as the film-forming sample 20, a square TiO ２ The (001) substrate was placed on the sample stage 21, and the heater 28 was operated to raise the temperature inside the film formation chamber 27 to 900° C. Next, the flow rate control valve 23 was opened to supply carrier gas from the carrier gas source 22 into the film formation chamber 27. After the atmosphere inside the film formation chamber 27 was sufficiently replaced with the carrier gas, the flow rate of the carrier gas was adjusted to 3 L / min. Oxygen gas was used as the carrier gas.

[0031] Next, the ultrasonic vibrator 26 was vibrated at 3.0 MHz, and the vibration was propagated to the atomization raw material liquid 24a through the ultrasonic transmitter 25a, thereby atomizing the atomization raw material liquid 24a to generate raw material fine particles. These raw material fine particles were introduced into the film formation chamber 27 by the carrier gas, reacted in the film formation chamber 27, and formed GeTiO 2 having a tetragonal rutile structure on the film formation sample 20 by a CVD reaction on the film formation surface of the film formation sample 20. ２ A crystal film having a thickness of 1.3 μm was formed.

[0032] The obtained crystalline film was measured using an X-ray diffractometer. The XRD analysis results are shown in Figure 3. As is clear from Figure 3, the obtained crystalline film is r-GeTiO 2 having a tetragonal rutile structure. ２ The film was crystalline. In addition, the GeTiO ２ A single crystal film was formed.

[0033] The surface of the obtained crystalline film was observed using an SEM. The SEM image is shown in Figure 4. As is clear from Figure 4, the GeTiO ２ Furthermore, when the surface of the obtained crystalline film was observed using EDS, it was found that the crystalline film had grown to a thickness of 100 μm over the entire surface, as is clear from FIG. ２ It was found that the pores were formed over an area of ​​more than 100m.

[0034] Furthermore, when the surface of the obtained crystal film was observed using an atomic force microscope (AFM), it was found that the surface roughness (RMS) based on JIS B0601 was 0.07 nm, as shown in Figure 6, and that the surface smoothness was excellent.

[0035] An ohmic electrode was formed on the obtained crystal film using indium as shown in Figure 7, and ohmic measurements were performed. The results are shown in Figure 8. As is clear from Figure 8, it was found that the film had excellent ohmic characteristics. Furthermore, Hall effect measurements showed that the carrier type was "p" and the electrical resistivity was 0.093 Ωcm.

[0036] The crystal film and laminated structure of the present invention are suitable for use in, for example, semiconductor devices.

[0037] 19 Film forming apparatus 20 Film forming sample 21 Sample stage 22a Carrier gas source 22b Dilution gas source 23a Flow rate control valve 23b Flow rate control valve 24 Raw material partition 24a Raw material liquid for atomization 24b Ultrasonic transmitting substrate 24c Stand 26 Ultrasonic vibrator 27 Film forming chamber 28 Heater 30 Atomization device 31 Guide partition 33 Dilution gas supply pipe 34 Carrier gas supply pipe 35 Ultrasonic transmitting liquid tank 36 Ultrasonic transmitting liquid 37 Film forming chamber 101a n-type semiconductor layer 101b n+ type semiconductor layer 102 p-type semiconductor layer 103 Metal layer 104 Insulator layer 105a Schottky electrode 105b Ohmic electrode 111a n-type semiconductor layer 111b n+ type semiconductor layer 114 Semi-insulating layer 115a Gate electrode 115b Source electrode 115c Drain electrode 118 Buffer layer 121a Wide band gap n-type semiconductor layer 121b Narrow band gap n-type semiconductor layer 121c N+ type semiconductor layer 123 P-type semiconductor layer 124 Semi-insulating layer 125a Gate electrode 125b Source electrode 125c Drain electrode 128 Buffer layer 129 Substrate 131a N- type semiconductor layer 131b First n+ type semiconductor layer 131c Second n+ type semiconductor layer 132 P-type semiconductor layer 134 Gate insulating film 135a Gate electrode 135b Source electrode 135c Drain electrode 138 Buffer layer 139 Semi-insulating layer 141a N- type semiconductor layer 141b First n+ type semiconductor layer 141c Second n+ type semiconductor layer 142 P type semiconductor layer 145a Gate electrode 145b Source electrode 145c Drain electrode 151 N type semiconductor layer 151a n- type semiconductor layer 151b n+ type semiconductor layer 152 P type semiconductor layer 154 Gate insulating film 155a Gate electrode 155b Emitter electrode 155c Collector electrode 161 N type semiconductor layer 162 P type semiconductor layer 163 Light emitting layer 165a First electrode 165b Second electrode 167 Light-transmitting electrode 169 Substrate 1010a N- type semiconductor 1010b N+ type semiconductor 1020 Ohmic electrode 1030 Schottky electrode 1030a Metal layer 1030b Metal layer 1030c Metal layer 1060 Electrolytic relaxation region

Claims

1. A crystal film containing as its main component a compound containing germanium, said compound further containing at least one metal element of Group 4 of the periodic table.

2. The crystal film according to claim 1, which has a tetragonal crystal structure.

3. 100mm ２ 2. The crystal film according to claim 1, having an area of ​​at least 100 nm.

4. The crystal film according to claim 1, having a thickness of 1 μm or more.

5. The crystalline film according to claim 1 which is a single crystal.

6. The crystal film according to claim 1, which has a surface roughness of 10 nm or less.

7. The crystalline film of claim 1, wherein said compound comprises titanium.

8. The crystal film according to claim 1, which has an electrical resistivity of 10 Ωcm or less.

9. The crystal film according to claim 1, which is a p-type semiconductor.

10. The crystal film according to claim 1, which forms an ohmic contact with a metal layer.

11. A crystal mainly composed of an oxide semiconductor having a rutile structure, the oxide semiconductor containing germanium and being a p-type semiconductor.

12. The crystal according to claim 11, which is in the form of a membrane.

13. A laminated structure in which a crystal film is laminated directly or via another layer on a crystal substrate, the crystal film being the crystal film according to claim 1 or the crystal according to claim 12.

14. A laminated structure in which an ohmic contact is formed between a metal layer and a crystal film, said crystal film being the crystal film of claim 1 or the crystal of claim 12.

15. The laminate structure according to claim 14, wherein the metal layer contains one or more metal elements selected from the d-block metal elements and / or p-block metal elements of the periodic table.

16. The laminate structure of claim 14, wherein said metal layer comprises indium.

17. A semiconductor device including a crystal film or a laminated structure, wherein the crystal film is the crystal film of claim 1 or the crystal of claim 12, and the laminated structure is the laminated structure of claim 13 or claim 14.

18. The semiconductor device according to claim 17, which is a power device.

19. The semiconductor device according to claim 17, which is a Schottky barrier diode (SBD), a junction barrier Schottky diode (JBS), a high electron mobility transistor (HEMT), a metal oxide semiconductor field effect transistor (MOSFET), a junction field effect transistor (JFET), an insulated gate bipolar transistor (IGBT) or a light emitting diode (LED).

20. An electronic device including a semiconductor device, characterized in that the semiconductor device is the semiconductor device according to claim 17.

21. A system including an electronic device, the electronic device being the electronic device of claim 20.

Images