Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/0405—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising semiconducting carbon, e.g. diamond, diamond-like carbon
  • H01L21/041—Making n- or p-doped regions
  • H01L21/0415—Making n- or p-doped regions using ion implantation
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/02—Elements
  • C30B29/04—Diamond
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/26—Bombardment with radiation
  • H01L21/263—Bombardment with radiation with high-energy radiation
  • H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
  • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
  • H10D62/83—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge
  • H10D62/834—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge further characterised by the dopants

Definitions

• the present invention relates to a method for producing an n-type semiconductor diamond by an ion implantation method and a low-resistance n-type semiconductor diamond.
• a method of producing low-negative n-type spheroidal diamond containing lithium (L i) and nitrogen (N) by ion implantation and a method of heat treatment of diamond to recover irradiation damage after ion implantation.
• Diamond is composed of carbon (C), a group IVb element of the same family as silicon (S i), which is widely used as a semiconductor material, and has a crystal structure similar to that of Si.
• C carbon
• S i silicon
• Can be seen as Diamond as a semiconductor material has a very large band gap of 5.5 eV, and the carrier mobility of both electrons and holes is as high as 2000 cN ⁇ ZV's at room temperature. Further, the dielectric constant is as small as 5.7, and the breakdown electric field is as large as 5 ⁇ 1 ovZcm. In addition, it has the rare property of negative electron affinity where the vacuum level exists below the bottom of the conduction band.
• diamond has excellent semiconductor properties, so that it can be used in high-temperature environments and in the space environment, can be used in environment-resistant devices, can operate high-frequency and high-power devices, and can emit ultraviolet light. Or, it is expected to be applied as a material for semiconductor devices such as electron emission devices that can be driven at low voltage.
• p-type and n-type conductivity control is required. Such control is performed by doping the semiconductor material with an impurity.
• an Si single crystal becomes n-type if phosphorus (P) is doped, and a p-type if boron (B) is doped.
• Typical doping methods for adding such impurities are (a) a method of doping by adding an impurity element during crystal growth, and (a) a thermal diffusion method of doping impurities by diffusion from the crystal surface.
• Crystallize accelerated impurity ions There is an ion implantation method for implanting from the surface. Among them, the ion implantation method can (1) accurately control the amount and depth of impurities to be added, (2) can control the doping region by using a photoresist in combination, (3) Compared to the thermal diffusion method, it has excellent characteristics such as less lateral diffusion of impurities, and is the mainstream of the current semiconductor doping process. However, if impurity ions are implanted into the crystal, the crystal structure will be destroyed. After the ion implantation, heat treatment and other steps must be performed to restore the crystal structure and electrically activate the implanted impurities. Must be inserted.
• CI RA was improved with some improvements.
• Appl. Phys. Lett. 68, P 2264 (1996) showed that the carrier concentration was 6 ⁇ 10 13 cm- 3 in Hall measurement at 300 K. It has been reported that ion implantation of 385 cmW ⁇ s could produce B-doped p-type diamond. These values are comparable to those of B-doped p-type epitaxial semi-rigid diamonds, and C IRA has made it possible to produce p-type semiconductor diamonds using an ion implantation process.
• n-type semiconductor diamond there have been many experiments of ion-implanting n-type dopants such as phosphorus (P) and sulfur (S) lithium (L i).
• Japanese Patent Application Laid-Open No. 11-100296 proposes a method of ion-implanting a Group V element to obtain an ⁇ -type.
• a method of heat treatment using a laser beam is disclosed.
• a method of irradiating ultraviolet rays for damage recovery and dopant activation has been proposed.
• they differ only in the method of providing the thermal energy required for the recovery of defects, and there is no description of the resistance value.
• Diamond and Realistic Materials 8 P 16 35 (1 9 As in 9 9), it is estimated that the resistance was very high.
• the present invention has been made to solve the above problems, and an object of the present invention is to provide a low-resistance n-type semi-red body diamond by an ion implantation method and a method of manufacturing the same. More specifically, after a predetermined amount of Li is ion-implanted into a diamond single crystal containing a predetermined amount of N, or a diamond single crystal substantially containing no impurities, Li and N are respectively specified. It is an object of the present invention to provide a method for obtaining an n-type semiconductor diamond by performing ion implantation at a given energy and dose and then performing a heat treatment in a predetermined temperature range.
• the method for producing an n-type semiconductor diamond of the present invention contains N at 1 O ppm or more.
• the diamond single crystal is ion-implanted so as to contain L i at least 1 Op pm to form a diamond containing L i and N, and then heat-treated at a temperature range of 800 ° C or more and less than 1800 ° C to obtain L It is characterized by electrical activation of i and N and recovery of diamond crystal structure.
• the difference between Li and N after the ion implantation is improved.
• Ion implantation is performed so that the ion implantation depths, each having a concentration of 10 ppm or more, overlap, and then heat treatment is performed at a temperature in the range of 800 ° C or more and less than 1800 ° C to electrically activate Li and N and diamond crystals.
• the feature is to recover the structure. For example, referring to FIG.
• the ion implantation depth where the Li concentration 1 is 1 Oppm or more is defined as The ion implantation depth is 0.11 to 0.20 m and the ion implantation depth when the N concentration 2 is 1 Oppm or more is 0.19 to 0.30 m. Therefore, the concentrations of Li and N are respectively 10 ppm or more in the ion implantation depth range of 0.19 to 0.28. The maximum overlap value of 10 is 0.25 for ion implantation depth and 170 ppm.
• Another method for producing an n-type semiconductor diamond of the present invention is that, when Li and N are ion-implanted into a diamond single crystal as an n-type dopant, the concentrations of Li and N after the ion implantation are respectively different from each other.
• the ion implantation is characterized in that the ion implantation depths of 10 ppm or more are overlapped and that the total dose of Li and N is 5.0 ⁇ 10 15 cm ⁇ 2 or less.
• the diamond single crystal to be ion-implanted is irradiated with an electron beam using an ion implanter having an electron beam line and two ion beam lines. It is preferable to implant N simultaneously.
• the method for producing an n-type semiconductor diamond of the present invention is characterized in that, in the step of recovering the crystal structure of diamond having irradiation damage after ion implantation and activating the dopant, under a high pressure condition of 3 GPa or more.
• the heat treatment is performed in a temperature range of 800 ° C. or more and less than 1800 ° C.
• the n-type quasi-half diamond according to the present invention is a diamond single crystal containing L i and N formed by an ion implantation method, wherein L i and N are at least 10 ppm at the same depth from the crystal surface. and contains, sheet resistance Ru der less 1 0 7 ⁇ / mouth.
• the sheet resistance of the n-type semi-your health diamond created by the manufacturing method is less 1 0 7 ⁇ / mouth, a practical resistance.
• FIG. 1 shows the concentration distribution of Li and N in the depth direction of the sample No. 1 of Example 1.
• FIG. 2 is a depth distribution of Li and N in the No. 23 sample of Example 2 in the depth direction.
• FIG. 3 shows the concentration distribution of Li and N in the depth direction of the sample No. 46 of Example 3.
• FIG. 4 shows the concentration distribution of Li and N in the depth direction of the sample of No. 47 in Example 3.
• FIG. 5 shows the concentration distribution in the depth direction of L i and N of the N 0 54 sample of Example 3.
• n-type semiconductor diamond implanted with P or S has high resistance even after heat treatment, because the crystallinity of diamond is recovered and the n-type dopant is combined with vacancies generated during ion implantation. This is considered to be because the n-type dopant is electrically inactivated.
• the present inventors have conducted intensive research to devise an ion implantation method in which the n-type dopant is not connected to the vacancies even after the heat treatment and is electrically activated. As a result, they have found that it is only necessary to implant ions into a N-containing diamond single crystal so as to contain Li at 1 O ppm or more. In the same manner, Li and N are ion-implanted into a diamond single crystal that does not substantially contain impurities, and the concentration of Li and N after ion implantation is 10 pp ni or more, respectively. It was found that the ions should be implanted so that the depths overlap.
• Li and N are ion-implanted into the diamond single crystal, and Li and N are implanted so that the ion implantation depths at which the concentrations of Li and N after ion implantation are respectively 10 ppm or more overlap each other. It has been found that the ion implantation should be performed so that the total dose is 5.0 X 10 i 5 cm- 2 or less.
• L i is an n-type dopant which exists between lattices in the diamond crystal and forms a donor.
• N is an n-type dopant that substitutes for a carbon atom in the diamond crystal and becomes a donor.
• N-containing diamond exists in nature and can also be made by artificial synthesis of diamond by high-temperature and high-pressure synthesis.
• the donor level of N is very deep, about 1: 7 eV, with respect to the band gap of diamond 5.5 eV, and is hardly activated at room temperature and has high resistance. .
• Li and N are likely to bond to each other, such that Li 3 N (lithium nitride) exists as a stable Li nitrogen compound.
• the inventors studied applying such properties of L i and N to n-type doping of diamond by ion implantation.
• the diamond single crystal containing N contains only Li or substantially impurities so that the diamond single crystal contains 10 ppm or more of Li and N at the same depth from the crystal surface. If Li and N are ion-implanted into a diamond single crystal that does not exist, when heat treatment is performed, Li and N undergo pairing before Li can associate with vacancies, and It has been found that it is a shallow donor that is electrically active without being connected to vacancies.
• the ion implantation depths in which the concentrations of Li and N after the ion implantation are respectively 10 ppm or more are overlapped, and the total dose of Li and N is 5.0 X 10 15 cm to 2 cm. If L i and N are ion-implanted as shown below, when heat treatment is performed, L i and N undergo pairing earlier than L i becomes associated with vacancies, and L i—N pairs Found that it was not electrically connected to the vacancies and became an electrically active shallow donor.
• L i and N are each set at the same depth from the crystal surface.
• an electron beam is irradiated to a diamond single crystal to be ion-implanted using an ion implanter having two ion beam lines and an electron beam line.
• the implanted ions lose their energy while colliding with the carbon atoms in the diamond crystal, causing an atomic-level phenomenon at Li and N at the same time.
• By supplying electrons to the crystal surface of a diamond single crystal to be ion-implanted by a beam it has been found that Li and N are distributed at positions within the diamond single crystal where pairing is likely to occur.
• the heat treatment condition is out of the range of 800 ° C. or more and less than 180 ° C., the crystallinity of diamond is not completely recovered. .
• any method such as electric furnace heating, infrared irradiation, ultraviolet irradiation, and laser irradiation may be used.
• the heat treatment condition is not less than 800 ° C and less than 180 ° C at 3 GPa or more, if the dose is implanted, it is difficult to recover irradiation damage by heat treatment.
• the crystallinity of the diamond is not completely recovered, or the crystallinity can be recovered, but a plurality of Li and N aggregate and become electrically inactive. Also over 8 GPa
• This heat treatment can also be used for recovery of irradiation damage and electrical activation when implanting ions such as N alone, P, S, As, Cl, Se, Na, K :, and Br. It is.
• Li and N are contained at the same depth from the crystal surface at the same depth of 10 ppm or more, respectively, and the sheet resistance value is 10 7 ⁇ / port or less. Low resistance n-type semiconductor diamond can be obtained.
• an ion implanter with a maximum accelerating voltage of 400 kV is used.
• the diamond single crystal to be ion-implanted is a (100) plane with a size of 2 mm x 2 mm and a high-temperature high-pressure synthesis of 0.3 mm in thickness. Ib type single crystal diamond was used.
• the ion implantation temperature was room temperature, and the implantation angle was 7 ° to prevent channeling of the implanted ions.
• the heat treatment after the ion implantation was performed under reduced pressure and high pressure.
• the sample was placed in an infrared lamp furnace, then reduced to a predetermined pressure, and then heated to a predetermined temperature.
• the heat treatment time is 30 minutes.
• the sample was pressurized to a predetermined pressure using an ultra-high pressure generator, and then heated to a predetermined temperature.
• the heat treatment time is 10 hours.
• the crystallinity is not recovered below 3 GPa, and a special ultra-high pressure generator is required at a pressure exceeding 8 GPa, which is not desirable from the viewpoint of cost and productivity.
• the heat treatment was performed under the condition of not less than GPa and not more than 8 GPa.
• Table 1 shows the experimental conditions. In Table 1, the column of keV indicates the ion implantation energy, and the column of cm- 2 indicates the dose.
• the evaluation of the ion-implanted diamond thus produced was performed as follows.
• the evaluation of crystallinity was performed by Raman spectroscopy, the evaluation of electrical characteristics was performed by the Hall effect measurement by Van der Pauw method, and the concentration distribution of Li and N in diamond crystals was performed by secondary ion mass spectrometry (S IMS). . '
• the electrode is first graphitized in the depth direction from the deepest part to the outermost surface of the Li and N implanted layers by Ar ion implantation, and the electrodes are electrically connected to the L ⁇ and ⁇ implanted layers from the outermost surface. Areas with a diameter of 200 m where contact can be made are formed at the four corners of the sample, and Ti, Pt, and Au are vapor-deposited on the graphitized areas in this order by 100 nm each using an electron beam. By contacting for 20 minutes, an ohmic contact was formed.
• FIG. 1 shows the concentration distribution in the depth direction of Sample No. 1 in Table 1.
• Table 1 shows the N concentration (ppm) contained in the single crystal diamond used and the injection peak concentration (m) and depth (m) of the concentration distribution in the depth direction of Li.
• the ion species to be implanted into I b-type single-crystal diamond and A r, the ion implantation energy formic scratch 300 keV, as dose 1.0 10 14 Ji 111-2, a further heat treatment conditions, pressure is 1. 3 X 10 - 4 P a, temperature except for using 1200 ° C, experiments were carried out and evaluated in the same manner as in example 1.
• N was contained in the single crystal diamond at 70 ppm, the depth of the Ar injection peak was 0.17 m, and the concentration was 90 ppm.
• Raman spectroscopy only the peak at 1333 cm- 1 was confirmed, confirming that the crystallinity of the diamond had recovered.
• the sheet resistance was as high as 1.OX10 14 ⁇ / port or more, and the carrier type could not be determined.
• the diamond single crystal into which Li and N are ion-implanted is a high-purity high-pressure IIa single crystal diamond synthesized by high-temperature and high-pressure synthesis with a thickness of 3 mm on a (100) plane with a size of 2 mm ⁇ 2 mm. Except for the ion implantation, the ion implantation conditions and the heat treatment conditions were the same as in Example 1. In the evaluation, the concentration distribution of Li and N in the depth direction was measured by SIMS, and the maximum value (ppm) and the depth ( ⁇ m) of the smaller concentration in the overlapped portion were checked. It was the same as in Example 1.
• Figure 2 shows the concentration distribution in the depth direction of Sample No. 23 in Table 2. Table 2 shows the ion implantation conditions for Li and N and the evaluation results.
• the temperature condition in the heat treatment is out of the temperature range of 800 ° C or more and less than 1800 ° C, the crystallinity of the diamond will not be completely recovered, and the 'graphite component remains, and the hole measurement cannot be performed. Nakata.
• the maximum accelerating voltage is a cooling / heating implantation stage that can be cooled to liquid nitrogen temperature (196 ° C) and can be heated from room temperature to 1400 ° C in about 10 seconds.
• a 400 kV ion implanter was used.
• the diamond single crystal to be ion-implanted has a high quality on a (100) face of a 2mm x 2mm (100) face and a (100) face of a 0.3mm thick high-temperature and high-pressure synthesized Ib type single crystal diamond.
• Epitaxially grown non-doped diamond with a film thickness of 3_tm was used.
• the implantation angle was set at 7 ° to prevent channeling of the implanted ions.
• Table 3 shows the ion implantation conditions. In Table 3,: a ⁇ ion implantation energy of keV, column CM_ 2 shows the de one's weight.
• the heat treatment was performed by CIRA.
• ion implantation is performed at an energy and dose such that the ion implantation depths at which the concentrations of Li and N are 1 O ppm or more each overlap, and the total dose of Li and N is 5
• OX 10 15 cm- 2 or less it was confirmed that irradiation damage was recovered by heat treatment, Li and N were electrically activated, and a low-resistance n-type semiconductor diamond was formed. .
• Example 4 Except that the ion implantation energy is 40 keV and the dose is 2.0 ⁇ 10 15 cm— 2 , the ion implantation energy is 300 keV and the dose is 1.0 ⁇ 10 15 cm ⁇ 2 , and the ion implantation is In the same manner as in Example 1, ions 1 and 8] were ion-injected. As a result, the overlapping depth of the concentration of Li and Ar was 0.17 wm and the concentration was 870 p pip. Raman spectroscopy showed only a peak of 1333 cm- 1 and confirmed that the crystallinity of the diamond had recovered. However, in the Hall effect measurement, it was determined to be n-type, but the sheet resistance was 9.3 ⁇ 10 1 (5 ⁇ / port), which was extremely high, and was not a practical n-type semi-reliant diamond. (Example 4)
• the maximum accelerating voltage is a cooling / heating implantation stage that can be cooled to liquid nitrogen temperature (196 ° C) and can be heated from room temperature to 1400 ° C in about 10 seconds.
• An ion implanter with two 400 kV ion beam lines and an electron beam line with a maximum acceleration voltage of 100 kV was used.
• the single crystal diamond to be ion-implanted is the same as in Example 3.
• a 2 mnix 2 mm x 0.3 mm high-temperature and high-pressure synthesized Ib-type single-crystal diamond made by epitaxially growing 3 im high-quality non-doped diamond (100) was used.
• the implantation angle was set to 7 ° for both Li and N.
• An electron beam with an energy of 50 keV was set at a beam current such that it was equal to the dose of Li and N, and the electron beam was irradiated simultaneously with the ion implantation of Li and N.
• the temperature during ion implantation was -97 ° C. Evaluation of the diamond after the heat treatment and the ion implantation was performed in the same manner as in Example 3.
• Table 4 shows the ion implantation conditions for Li and N and the evaluation results. Table 4
• the ion implantation energy was 40 keV and the dose amount was 2.0 ⁇ 10 15 cm— 2, and that the ion implantation energy was 300 keV and the dose amount was 1.0 ⁇ 10 15 cm ⁇ 2 , the ion implantation was performed.
• L i and Ar were ion-implanted.
• the overlap depth of the concentration distributions of Li and Ar was 0.18 Mm, and the concentration was 850 p.
• Raman spectroscopy revealed that the peak was only at 1333 cm- 1 and that the diamond crystallinity had recovered. But, In the Hall effect measurement, it was determined to be n-type, but the sheet resistance was very low, 9.5 ⁇ 10 10 ⁇ , which was not a practical n-type semiconductor diamond. (Example 5).
• the diamond single crystal to be ion-implanted was a high-temperature and high-pressure synthesized I Ia type diamond.
• the size is 2 mm X 2 mm and the thickness is 0.3 mm.
• the 2X 2mm surface was (100).
• the temperature conditions for the ion implantation were room temperature (27 ° C), and the heat treatment was performed under the pressure of 3 GPa or more and 800 ° C or more and less than 1800 ° C.
• the diamond was evaluated.
• Table 5 shows ion implantation conditions and evaluation results
• Table 6 shows heat treatment conditions. In the heat treatment, the sample was pressurized to a predetermined pressure using an ultrahigh pressure generator, and then heated to a predetermined temperature. The heat treatment time is 10 hours. -Table 5
• the diamond after ion implantation is heat-treated at a temperature of 800 ° C or more and less than 1800 ° C under a pressure of 3 GPa or more,
• the irradiation damage is recovered, and Li and N are electrically activated to form a low-resistance n-type semiconductor diamond. confirmed.
• Ion-implanted diamond was prepared and evaluated in the same manner as in Example 5 except that the ion implantation conditions for Li and ⁇ were the same as in No. 73 in Table 5, and the heat treatment conditions were the same as those shown in Table 7. Table 7 shows the results. Table 7
• the maximum accelerating voltage is a cooling / heating implantation stage that can be cooled to liquid nitrogen temperature (196 ° C) and can be heated from room temperature to 1400 ° C in about 10 seconds.
• An ion implanter with two 400 kV ion beam lines and an electron beam line with a maximum acceleration voltage of 100 kV was used.
• the diamond single crystal to be ion-implanted was a high-temperature and high-pressure synthesized I Ia type diamond.
• the size is 2mm X 2mm and the thickness is 0.3mm.
• the 2 x 2 mm surface was (100).
• the temperature condition for ion implantation was -97 ° C, and Li and N were simultaneously ion-implanted using two ion beam lines.
• the injection angle was set to 7 ° for both Li and N to prevent channeling, and the beam current value was set so that the electron beam with an energy of 50 keV was equal to the total dose of Li and N. Irradiation was performed simultaneously with Li and N ion implantation.
• Ion implantation and diamond evaluation were performed in the same manner as in Example 3, except that the heat treatment was performed at a pressure of 3 GPa or more and a temperature of 800 ° C. or more and less than 1800 ° C.
• Table 8 shows ion implantation conditions and evaluation results
• Table 9 shows heat treatment conditions.
• the sample was pressurized to a predetermined pressure using an ultrahigh pressure generator, and then heated to a predetermined temperature. The heat treatment time is 10 hours.
• Li and N are simultaneously irradiated while irradiating the electron beam to the diamond to be ion-implanted, and the ion implantation depths where the concentrations of Li and N are each 10 ppm or more overlap.
• the ion-implanted diamond is heat-treated under a pressure of 3 GPa or more at a temperature of 800 ° C or more and less than 1800 ° C so that irradiation damage cannot be recovered by the conventional heat treatment method.
• the irradiation damage was recovered, and Li and N were electrically activated.
• the 1 and 1 ⁇ ions were simultaneously implanted, and compared to the case without electron beam irradiation. It was confirmed that n-type semiconductor diamond with lower resistance was formed.
• Li and Ar were ion-implanted in the same manner as in Example 7, except that the heat treatment was performed at a temperature of 1200 ° C. and a pressure of 6. OGP a.
• the overlap depth of the concentration distributions of Li and Ar was 0.16, and the concentration was 890 p.
• Raman spectroscopy only the peak at 1333 cm- 1 was confirmed, confirming that the crystallinity of the diamond had recovered.
• a diamond single crystal is made to contain L i and N by an ion implantation method, and is heat-treated in a predetermined temperature range so that L i and N
• a low-resistance n-type semiconductor diamond can be produced.
• n-type semiconductor diamonds have excellent semiconductor properties, so they can be used in high-temperature environments or space environments, can be used in environment-resistant devices, can operate at high frequencies and have high power, and can emit ultraviolet light. It can be applied as a material for semiconductor devices such as light emitting devices or electron emission devices that can be driven at low voltage.

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