CN211016566U - Monocrystalline diamond n-i-p nodule power battery - Google Patents
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Abstract
The utility model aims at providing a single crystal diamond n-i-p tuberculosis power battery has solved the current diamond schottky junction nuclear power battery and has opened a way the voltage low, the little problem of output current to promote diamond nuclear power battery's performance and application prospect. The single crystal diamond n-i-p nodule power battery comprises an intrinsic single crystal diamond substrate, an n-type diamond layer, an i-type diamond layer, a p-type diamond layer and a p-type ohmic electrode which are arranged in a laminated contact mode; on the surface of the n-type diamond layer, which is in contact with the i-type diamond layer, one part of the surface is in contact with the i-type diamond layer, and the other part of the surface is in contact with the n-type ohmic electrode; the p-type ohmic electrode is connected with the i-type diamond layer through a lead; the radiation source is arranged above the p-type ohmic electrode or arranged outside the i-type diamond layer in a surrounding mode.
Description
[ technical field ] A method for producing a semiconductor device
The utility model belongs to the technical field of semiconductor energy device, concretely relates to single crystal diamond n-i-p tuberculosis power battery.
[ background of the invention ]
Nuclear power cells come in a variety of classes, with radiant volt-effect energy conversion cells using semiconductor technology being more common. Early radiant volt-effect energy conversion cells dominated silicon and AlGaAs, but due to the high radiant energy, the cell material damage was large, causing the cell performance to degrade dramatically in a short time. In recent years, semiconductor materials with high radiation damage resistance are used for preparing nuclear power batteries, such as silicon carbide, gallium nitride and the like. Compared with silicon carbide and gallium nitride, diamond material has higher radiation damage resistance, so that the diamond material is the most suitable material for preparing nuclear power batteries. Meanwhile, the forbidden band width of the diamond material is also larger, and the theoretical conversion efficiency of the diamond material is also higher. Due to the limitation of n-type doping technology, the diamond nuclear power battery is mainly based on a p-type Schottky diode structure. However, the schottky junction has a low barrier height, which makes the open circuit voltage of the battery small, and the high resistance of diamond makes the reverse bias current small, which affects the output characteristics.
[ Utility model ] content
The utility model aims at providing a single crystal diamond n-i-p tuberculosis power battery to solve current diamond schottky junction nuclear power battery open circuit voltage low, the little problem of output current, thereby promote diamond nuclear power battery's performance and application prospect.
The utility model adopts the following technical scheme: a single crystal diamond n-i-p nodule power battery comprises an intrinsic single crystal diamond substrate, an n-type diamond layer, an i-type diamond layer, a p-type diamond layer and a p-type ohmic electrode which are arranged in a laminated contact mode; on the surface of the n-type diamond layer, which is in contact with the i-type diamond layer, one part of the surface is in contact with the i-type diamond layer, and the other part of the surface is in contact with the n-type ohmic electrode; the p-type ohmic electrode is connected with a battery anode through a lead, and the i-type diamond layer is connected with a battery cathode through a lead; the radiation source is arranged above the p-type ohmic electrode or arranged outside the i-type diamond layer in a surrounding mode.
Further, the radiation source does not contact both the n-type ohmic electrode and the p-type ohmic electrode.
Further, when the radioactive source is arranged on the upper side of the p-type ohmic electrode, the thickness of the i-type diamond layer is between 5 and 30 microns; when the radioactive source is arranged around the outside of the i-diamond layer, the diameter of the i-diamond is between 20 and 100 μm.
Further, the n-type ohmic electrode is a high-melting-point metal.
The volume ratio of phosphorus to carbon in the growth atmosphere of the n-type diamond layer is more than 0.01 percent, and the growth thickness of the n-type diamond layer is 50-200 nm.
Further, a layer of type i diamond at O2/H2The volume ratio is 0-1%, and the growth temperature is 900-1100 ℃.
Further, the p-type diamond layer is a boron doped layer with the doping concentration ND being more than or equal to 1019cm-3The thickness is 50-200 nm.
Furthermore, the p-type ohmic electrode is made of metal capable of forming carbide with the surface of the diamond, and the annealing treatment temperature is 500-700 ℃, and the annealing time is more than 10 min.
The utility model has the advantages that: the output voltage of the diamond nuclear power battery is effectively improved by adopting an n-i-p structure. Meanwhile, the i-type diamond layer grows on the n-type diamond layer through a mask, so that metal and the n-type diamond form good ohmic contact under the action of high temperature and plasma bombardment, the problem that the ohmic contact between the metal and the n-type diamond is difficult in the prior art is solved, and the output current of the diamond n-i-p nodule power battery can be improved.
[ description of the drawings ]
FIG. 1 is a schematic diagram of a diamond n-i-p nodule power battery with a radiation source arranged on the upper side of a p-type ohmic electrode;
FIG. 2 is a schematic diagram of a diamond n-i-p nodule power battery with a radiation source arranged on the side of an i-type diamond layer;
fig. 3 is a schematic structural diagram of a diamond n-i-p nodule power battery in embodiment 3 of the present invention.
Wherein, 1, intrinsic single crystal diamond substrate; a layer of n-type diamond; an n-type ohmic electrode; a layer of type i diamond; a p-type diamond layer; a p-type ohmic electrode; 7. a radioactive source; 8. a lead wire; 9. a battery positive electrode; 10. a battery negative electrode; 11. and a battery case.
[ detailed description ] embodiments
The present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
The utility model provides a monocrystalline diamond n-i-p nodule power battery, which comprises an intrinsic monocrystalline diamond substrate 1, an n-type diamond layer 2, an i-type diamond layer 4, a p-type diamond layer 5 and a p-type ohmic electrode 6 which are arranged in a laminated contact manner; on the surface of the n-type diamond layer 2 contacted with the i-type diamond layer 4, a part of the surface is contacted with the i-type diamond layer 4, and the rest part is contacted with the n-type ohmic electrode 3; in practice, the n-type ohmic electrode 3 may be provided in a circular hole shape, and the i-type diamond layer 4 and the p-type diamond layer 5 may be provided in the circular hole of the n-type ohmic electrode 3.
The p-type ohmic electrode 6 is connected with a battery anode 9 through a lead 8, and the i-type diamond layer 4 is connected with a battery cathode 10 through the lead 8; the solar cell further comprises a radioactive source 7, wherein the radioactive source 7 is arranged above the p-type ohmic electrode 6 or arranged outside the i-type diamond layer 4 in a surrounding mode.
The intrinsic single crystal diamond substrate 1 may be a high-temperature high-pressure synthetic substrate, a CVD synthetic substrate, or a self-supporting diamond film. The intrinsic single crystal diamond substrate 1 has a rectangular, circular, oval or other shape.
The n-type diamond layer 2 is doped with phosphorus and is obtained by an MPCVD epitaxial technology, and in order to enable phosphorus atoms to have the function of inducing surface reconstruction, the epitaxy is needed in an environment with a high phosphorus/carbon ratio, the volume ratio of phosphorus/carbon in a growth atmosphere is required to be more than 0.01 percent, and the growth thickness is 50-200 nm. After the growth is finished, the surface hydrogen terminal is oxidized into an oxygen terminal by heating with sulfuric acid/nitric acid at a ratio of 1:1 at a temperature higher than 200 ℃ or by ultraviolet ozone treatment, and the high-conductivity surface is obtained by annealing at a temperature higher than 900 ℃ for more than 5 min.
The n-type ohmic electrode 3 need only overlie a portion of the surface of the n-type diamond layer 2 and so in practice the n-type ohmic electrode 3 may be formed as a circular hole electrode for subsequent selective growth of the i-type diamond layer 4 and the p-type diamond layer 5 within the region of the holes thereof. In order to maintain the integrity of the n-type ohmic electrode 3 during the growth process, it is required that the melting point of the metal used is high and the metal does not play a role in catalyzing the generation of other carbon materials during the epitaxial growth process.
The i-type diamond layer 4 is the main working area of the nuclear power cell. Under the action of the ray particles, the i-type diamond layer 4 generates electron-hole pairs, and then the electron-hole pairs move to the n-type diamond layer 2 and the p-type diamond layer 5 respectively under the action of the built-in potential difference to form a potential difference, so that power is supplied to an external circuit. Therefore, the quality of the i-type layer needs to be high. The method of epitaxially growing the i-type diamond layer 4 on the n-type diamond 2 can solve the problem that the quality of the i-type layer is degraded by the dopant in the traditional process. During the growth of the i-type diamond layer 4, at O2/H2Growing under the condition of 0-1% of volume ratio to further improve the quality of the film. The size of the i-type diamond layer is required for efficient absorption of the radiation particles and conduction. When the radioactive source 7 is arrangedWhen placed on the upper side of the p-type ohmic electrode 6, the thickness of the i-type diamond layer 4 is required to be between 5 and 30 μm. When the radiation source 7 is placed on the side of the i-diamond layer, it is required that the i-diamond has a diameter of 20-100 μm.
The p-type diamond layer 5 needs to be heavily doped to form a good ohmic contact and a higher built-in potential difference to increase the open circuit voltage and output current. The boron doping concentration ND in the p-type diamond layer 5 is required>1019cm-3And has a thickness of 50-200nm in order to reduce the absorption of the radiation particles. After the growth is finished, the surface hydrogen terminal needs to be oxidized into an oxygen terminal by adopting an ultraviolet ozone treatment mode.
In order to form a good ohmic contact, the p-type ohmic electrode 6 is required to be metal capable of forming carbide with the surface of diamond, such as titanium, tungsten and the like, and is required to be annealed in an inert protective gas atmosphere, wherein the annealing temperature is 500-700 ℃, and the annealing time is more than 10 min. The shape of the p-type ohmic electrode 6 may be circular, rectangular or other shapes.
The radioactive source 7 is arranged above the p-type ohmic electrode 7 or surrounds the outer side surface of the i-type diamond layer 4. To increase the battery life, the half-life of the radioactive source is required to be longer than 20 years.
For safety, it is necessary to package the device with a battery case 11 capable of shielding radiation, connect the p-type ohmic electrode 7 to the battery positive electrode 9 with a lead 8, and connect the n-type ohmic electrode 3 to the battery negative electrode 10 with a lead 8.
The utility model discloses a preparation method of single crystal diamond n-i-p tuberculosis power battery, including following step:
growing an n-type diamond layer 2 on an intrinsic single crystal diamond substrate 1 in a high phosphorus/carbon ratio atmosphere by adopting microwave plasma chemical vapor deposition, oxidizing a hydrogen terminal on the surface of the n-type diamond layer 2 into an oxygen terminal through oxidation treatment, and annealing at the temperature of more than 900 ℃ for more than 5min to obtain a high-conductivity surface;
step two, dividing two partial areas on the high-conductivity surface:
preparing a tungsten electrode on the surface of the n-type diamond layer 2 as an n-type ohmic electrode 3 on a part of area through photoetching, magnetron sputtering and stripping processes;
on the other part of the area, sequentially growing an i-type diamond layer 4 and a p-type diamond layer 5 upwards by adopting microwave plasma chemical vapor deposition, and oxidizing the surface hydrogen terminal of the p-type diamond layer 5 into an oxygen terminal by oxidation treatment;
thirdly, preparing a p-type ohmic electrode 6 on the surface of the p-type diamond layer 5, and forming ohmic contact through annealing;
and fourthly, arranging a radioactive source 7 above the p-type ohmic electrode 6 or around the outer side of the i-type diamond 4, connecting the p-type ohmic electrode 6 with a battery anode 9 by a lead 8, connecting the n-type ohmic electrode 3 with a battery cathode 10 by the lead 8, and packaging the whole by using a battery shell 11.
Wherein, the n-type ohmic electrode 3 is a high melting point metal. And the volume ratio of phosphorus to carbon in the growth atmosphere of the n-type diamond layer 2 is more than 0.01 percent, the growth thickness of the n-type diamond layer is 50-200nm, and after the growth is finished, the surface hydrogen terminal is oxidized into the oxygen terminal by heating with sulfuric acid/nitric acid at a ratio of 1:1 at a temperature of more than 200 ℃ or by adopting ultraviolet ozone treatment. The i-type diamond layer 4 grows under the condition that the volume ratio of O2/H2 is 0-1%, and the growth temperature is between 900 ℃ and 1100 ℃. And the p-type diamond layer 5 is a boron doped layer, the doping concentration ND is more than or equal to 1019cm-3, the thickness is 50-200nm, and in the second step, the surface hydrogen terminal of the p-type diamond layer 5 is oxidized into an oxygen terminal in an ultraviolet ozone treatment mode. The p-type ohmic electrode 6 is a metal capable of forming carbide with the surface of the diamond, the annealing temperature is 500-700 ℃, and the annealing time is more than 10 min.
Example 1
As shown in figure 1, the intrinsic single crystal diamond substrate 1 of the single crystal diamond n-i-p nodule power battery is a high-temperature and high-pressure synthesized single crystal diamond with the size of 3 × 3 × 0.3.3 mm3. An n-type diamond layer 2 with the thickness of 200nm is epitaxially grown on the surface of the substrate by an MPCVD method, and the growth conditions are as follows: gas pressure 100Torr, gas flow rate 500sccm, CH4/H2＝1％，PH3/CH40.1%, the substrate temperature was 900 ℃. After the growth is finished, putting the sample into a mixed solution of sulfuric acid and nitric acid with the ratio of 1:1, and 2Heating at 50 deg.C for 1h to convert surface hydrogen termination to oxygen termination, and annealing at 1000 deg.C for 5min to obtain high-conductivity surface.
And preparing a round hole type tungsten electrode on the surface of the n-type diamond layer 2 as an n-type ohmic electrode 3 through photoetching, magnetron sputtering and stripping processes, wherein the thickness of the electrode is 100 nm. Then, using the MPCVD method, a 10 μm i-type diamond layer 4 and a 100nm p-type diamond layer 5 were grown in that order in the areas not covered by the metallic tungsten. The growth conditions of the i-type diamond layer 4 are as follows: gas pressure 80Torr, gas flow rate 500sccm, CH4/H2＝1％， O2/H20.05%, the substrate temperature was 900 ℃.
The growth conditions for the p-type diamond layer 7 were: gas pressure 80Torr, gas flow rate 500sccm, CH4/H2＝1％，TMB/CH410000ppm, 900 ℃ substrate temperature, 1019cm doping concentration-3. After growth is finished, ultraviolet ozone treatment is carried out on the sample, and the surface hydrogen terminal is converted into an oxygen terminal.
And preparing a round titanium electrode on the surface of the p-type diamond layer 5 as a p-type ohmic electrode 6 by photoetching, magnetron sputtering and stripping processes, and annealing for 30min at 500 ℃ in an argon environment to obtain good ohmic contact. And placing the radioactive source 7 on the upper side of the p-type ohmic electrode 6, packaging by using a battery shell 11, connecting the p-type ohmic electrode 7 with a battery anode 9 by using a lead 8, and connecting the n-type ohmic electrode 3 with a battery cathode 10 by using the lead 8 to obtain the diamond n-i-p nodule power diode.
Example 2
As shown in FIG. 2, the intrinsic single crystal diamond substrate 1 of the single crystal diamond n-i-p nodule power battery is CVD synthesized single crystal diamond with the size of 2 × 2 × 0.2mm3. An n-type diamond layer 2 with the thickness of 100nm is epitaxially grown on the surface of the substrate by an MPCVD method, and the growth conditions are as follows: gas pressure 100Torr, gas flow rate 500sccm, CH4/H2＝1％，PH3/CH40.5%, the substrate temperature was 900 ℃. After growth is finished, the surface hydrogen terminal is converted into an oxygen terminal by adopting ultraviolet ozone treatment, and annealing is carried out for 10min at 900 ℃ to obtain a high-conductivity surface.
And preparing a round hole type tungsten electrode on the surface of the n-type diamond layer 2 as an n-type ohmic electrode 3 through photoetching, magnetron sputtering and stripping processes, wherein the thickness of the electrode is 50nm, and the diameter of a round hole is 30 mu m. Then, using the MPCVD method, a 40 μm i-type diamond layer 4 and a 100nm p-type diamond layer 5 were grown in that order in the areas not covered by metallic tungsten. The growth conditions of the i-type diamond layer 4 are as follows: gas pressure 80Torr, gas flow rate 500sccm, CH4/H2＝1％，O2/H20.1%, the substrate temperature was 900 ℃.
The growth conditions for the p-type diamond layer 7 were: gas pressure 80Torr, gas flow rate 500sccm, CH4/H2＝1％，TMB/CH420000ppm, the substrate temperature is 900 ℃, and the final doping concentration is 1019cm-3. After growth is finished, ultraviolet ozone treatment is carried out on the sample, and the surface hydrogen terminal is converted into an oxygen terminal.
And preparing a round titanium electrode on the surface of the p-type diamond layer 5 as a p-type ohmic electrode 6 through photoetching, magnetron sputtering and stripping processes, and annealing for 30min at 600 ℃ in an argon environment to obtain good ohmic contact. And (3) arranging a radioactive source 7 on the outer side surface of the i-type diamond layer 4 in a surrounding manner, packaging the radioactive source by using a battery shell 11, connecting the p-type ohmic electrode 7 with a battery anode 9 by using a lead 8, and connecting the n-type ohmic electrode 3 with a battery cathode 10 by using the lead 8 to obtain the diamond n-i-p nodule power diode.
Example 3
As shown in FIG. 3, the intrinsic single crystal diamond substrate 1 of the single crystal diamond n-i-p nodule power battery is CVD synthesized single crystal diamond with the size of 5 × 5 × 0.5.5 mm3. And epitaxially growing an n-type diamond layer 2 with the thickness of 50nm on the surface of the substrate by adopting an MPCVD method, wherein the growth conditions are as follows: gas pressure 100Torr, gas flow rate 500sccm, CH4/H2＝1％，PH3/CH 41%, the substrate temperature was 900 ℃. After growth is finished, the surface hydrogen terminal is converted into an oxygen terminal by adopting ultraviolet ozone treatment, and annealing is carried out for 5min at 1100 ℃ to obtain a high-conductivity surface.
Preparing a strip-shaped tungsten electrode on the surface of the n-type diamond layer 2 as an n-type ohm through photoetching, magnetron sputtering and stripping processesAnd the thickness of the electrode 3 is 50nm, the width is 2.5mm, and the length is 5 mm. Then, using the MPCVD method, a 40 μm i-type diamond layer 4 and a 100nm p-type diamond layer 5 were grown in that order in the areas not covered by metallic tungsten. The growth conditions of the i-type diamond layer 4 are as follows: gas pressure 80Torr, gas flow rate 500sccm, CH4/H2＝1％，O2/H20.1%, the substrate temperature was 900 ℃.
The growth conditions for the p-type diamond layer 7 were: gas pressure 80Torr, gas flow rate 500sccm, CH4/H2＝1％，TMB/CH4100000ppm, substrate temperature 900 deg.C, and final doping concentration of 1020cm-3. After growth is finished, ultraviolet ozone treatment is carried out on the sample, and the surface hydrogen terminal is converted into an oxygen terminal. And preparing a round titanium electrode on the surface of the p-type diamond layer 5 as a p-type ohmic electrode 6 through photoetching, magnetron sputtering and stripping processes, and annealing for 30min at 600 ℃ in an argon environment to obtain good ohmic contact. And placing a radioactive source 7 on the side surface of the i-type diamond layer 4, packaging by using a battery shell 11, connecting the p-type ohmic electrode 7 with a battery anode 9 by using a lead 8, and connecting the n-type ohmic electrode 3 with a battery cathode 10 by using the lead 8 to obtain the diamond n-i-p nodule power diode.
Due to the limitation of n-type doping technology, the diamond nuclear power battery is mainly based on a p-type Schottky diode structure. However, the schottky junction has a low barrier height, which makes the open circuit voltage of the battery small, and the high resistance of diamond makes the reverse bias current small, which affects the output characteristics. The utility model discloses mask growth i type diamond layer on n type diamond layer can make metal and n type diamond form good ohmic contact under the effect of high temperature and plasma bombardment, has solved the difficult problem of metal and n type diamond ohmic contact among the prior art. After the problem of metal among the prior art and the difficult ohmic contact of n type diamond is solved, the utility model discloses adopt n-i-p structure preparation nuclear power battery promptly. For the n-i-p diode, the generation of the photo-generated electromotive force aims at balancing the built-in potential difference, and the larger the built-in potential difference is, the larger the photo-generated electromotive force is; the theoretical value of the built-in potential difference of the diamond n-i-p junction is 4.51V which is far higher than that of other materials, so that the larger the photo-generated electromotive force is, the higher the voltage applied to an external circuit is, and the larger the current is. Therefore, the nuclear power battery prepared by the n-i-p structure can effectively improve the output voltage and the output current of the battery, solves the problems of low open-circuit voltage and small output current of the conventional diamond Schottky junction nuclear power battery, and is a novel nuclear power battery with high performance and wide application prospect.
Claims (8)
1. The monocrystalline diamond n-i-p nodule power battery is characterized by comprising an intrinsic monocrystalline diamond substrate (1), an n-type diamond layer (2), an i-type diamond layer (4), a p-type diamond layer (5) and a p-type ohmic electrode (6) which are arranged in a laminated contact manner; on the surface of the n-type diamond layer (2) contacted with the i-type diamond layer (4), one part is contacted with the i-type diamond layer (4), and the other part is contacted with the n-type ohmic electrode (3); the p-type ohmic electrode (6) is connected with a battery anode (9) through a lead (8), and the i-type diamond layer (4) is connected with a battery cathode (10) through the lead (8); the solar cell further comprises a radioactive source (7), wherein the radioactive source (7) is arranged above the p-type ohmic electrode (6) or arranged on the outer side of the i-type diamond layer (4) in a surrounding mode.
2. A single crystal diamond n-i-p nodule power cell as claimed in claim 1 wherein the radiation source (7) is not in contact with both the n-type ohmic electrode (3) and the p-type ohmic electrode (6).
3. A single crystal diamond n-i-p nodule power cell as claimed in claim 1 or 2 wherein the thickness of the i-type diamond layer (4) is between 5 and 30 μm when the radiation source (7) is positioned on top of the p-type ohmic electrode (6); when the radioactive source (7) is arranged around the outer side of the i-type diamond layer, the diameter of the i-type diamond is 20-100 μm.
4. A single crystal diamond n-i-p nodule power cell as claimed in claim 1 or 2, wherein the n-type ohmic electrode (3) is a refractory metal.
5. A single crystal diamond n-i-p nodule power cell as claimed in claim 1 or 2 wherein the n-type diamond layer (2) has a phosphorus/carbon volume ratio in the growth atmosphere of greater than 0.01% and a growth thickness of 50 to 200 nm.
6. A single crystal diamond n-i-p nodule power cell as claimed in claim 1 or 2 wherein the i type diamond layer (4) is O2/H2The volume ratio is 0-1%, and the growth temperature is 900-1100 ℃.
7. The monocrystalline diamond n-i-p nodule power cell as claimed in claim 1 or 2, wherein the p-type diamond layer (5) is a boron doped layer with a doping concentration ND > 1019cm-3The thickness is 50-200 nm.
8. The single crystal diamond n-i-p nodule power cell as defined in claim 1 or 2 wherein the p-type ohmic electrode (6) is made of a metal capable of forming carbide with the diamond surface, and the annealing temperature is 500-700 ℃ and the annealing time is 10min or more.
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