CN113461717B - Organomagnesium compound and electronic device - Google Patents
Organomagnesium compound and electronic device Download PDFInfo
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- CN113461717B CN113461717B CN202111036678.1A CN202111036678A CN113461717B CN 113461717 B CN113461717 B CN 113461717B CN 202111036678 A CN202111036678 A CN 202111036678A CN 113461717 B CN113461717 B CN 113461717B
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- 150000002901 organomagnesium compounds Chemical class 0.000 title claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910016420 Ala Inb Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 53
- 239000011777 magnesium Substances 0.000 abstract description 53
- 150000002681 magnesium compounds Chemical class 0.000 abstract description 21
- 239000002019 doping agent Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 15
- 238000000407 epitaxy Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052733 gallium Inorganic materials 0.000 abstract description 4
- 150000004767 nitrides Chemical class 0.000 description 44
- 239000012298 atmosphere Substances 0.000 description 34
- 229910002601 GaN Inorganic materials 0.000 description 20
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000003780 insertion Methods 0.000 description 7
- 230000037431 insertion Effects 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 2
- -1 methylcyclopentadienyl structures Chemical group 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
Abstract
The present application provides an organomagnesium compound having a structure represented by the following structural formula (1):
the organic magnesium compound in the structural formula (1) is liquid in a working state, has stable high saturated vapor pressure, and is very suitable for being used as a magnesium source dopant for semiconductor doping; in the magnesium source process, the magnesium component is uniformly distributed, so that the epitaxy uniformity and the production process stability are improved, and the method is suitable for large-size substrate epitaxy; on the other hand, the vapor pressure is very stable in the last stage of the use of the magnesium source, so that the use efficiency and the mobility of gallium production are improved, the production cost is reduced, and the method is suitable for large-scale mass production.
Description
Technical Field
The application relates to the field of metal organic compounds, in particular to an organic magnesium compound and an electronic device.
Background
The third generation semiconductor material mainly comprises gallium nitride and silicon carbide, the production process comprises three major steps of single crystal growth, epitaxial layer growth and device manufacturing, and large links such as industrial chain substrates, epitaxy, devices and modules correspond to the production process.
Epitaxy is an intermediate link at the core of the whole industry chain, the performance of a device is directly influenced by an epitaxy process technology, and a very critical effect is played on the development of the industry, a metal organic compound is a key supporting raw material of the epitaxy technology, and the purity and the vapor pressure stability of the metal organic compound directly determine the performance of the device, so that the technical development of the metal organic compound plays a very critical role on the development of the industry.
Magnesium is generally used as a dopant in the epitaxial growth P-type gallium nitride technology, magnesium cyclopentadienyl is the most commonly used magnesium source, the melting point is more than 170 ℃, colorless crystals are formed at normal temperature and normal pressure, and as a solid source, magnesium cyclopentadienyl has many limitations, for example, because the surface area of product particles is small, and 'channeling' is easily generated in a steel cylinder, the vapor pressure is unstable, the doping concentration of the prepared chip magnesium is not uniform, and the use ratio of magnesium cyclopentadienyl is lower than 20%.
The solid magnesium metallocene can not meet the requirement of the prior art for large-flow magnesium source steam. To solve the problem, the prior art generally optimizes the substituent on the metallocene ring or the form of the metallocene, for example, chinese patent document (application publication No. CN112004959A, application publication date: 11/27/2020) discloses a magnesium compound suitable for atomic layer deposition method, which maintains the whole structure of the metallocene, and simultaneously replaces one hydrogen atom on the metallocene ring with isopropyl, sec-butyl or tert-butyl, but the magnesium compound is only suitable for atomic layer deposition method. Chinese patent document (application publication No. CN1399006A, application publication date: 26/2/2003) discloses a method for preparing a solution magnesium source by dispersing magnesium diclometer or magnesium dimethyldiclometer in a solvent to form a high concentration solution magnesium source instead of solid magnesium diclometer, but the method inevitably introduces a solvent which interferes with the epitaxial process.
Therefore, the development of a stable magnesium source having a high saturation vapor pressure and a high utilization rate is of great significance for the manufacture of semiconductor devices.
Disclosure of Invention
The present application provides an organomagnesium compound of a novel structure, which has a stable high saturated vapor pressure and a high usage rate.
One aspect of the present application provides an organomagnesium compound having a structure represented by the following structural formula (1):
In another aspect, the present application provides an electronic device comprising an epitaxial layer containing a doping of magnesium atoms provided by an organomagnesium compound represented by structural formula (1).
In one embodiment, the epitaxial layer is AlaInbGa1-a-bAnd N layers, wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, a + b is more than or equal to 0 and less than or equal to 1, and the values of a and b are constant, linear or nonlinear.
In one embodiment, the AlaInbGa1-a-bThe doping concentration of the N layer is 1 × 1018Per cm3To 5X 1020Per cm3In the meantime.
In one embodiment, the electronic device is a light emitting diode, a transistor, a laser, a detector, or a solar cell.
Has the advantages that: in the application, the organic magnesium compound is liquid in a working state, has stable high saturated vapor pressure, and is very suitable for being used as a magnesium source dopant for semiconductor doping; in the magnesium source process, the magnesium component is uniformly distributed, so that the epitaxy uniformity and the production process stability are improved, and the method is suitable for large-size substrate epitaxy; on the other hand, the vapor pressure is very stable in the last stage of the use of the magnesium source, so that the use efficiency and the gallium production mobility are improved, the production cost is reduced, and the method is suitable for large-scale mass production of electronic devices.
Drawings
Certain specific embodiments of the present application will hereinafter be described in detail by way of example and not limitation with reference to the accompanying drawings, in which like reference numerals identify the same or similar parts or features, and it will be appreciated by those skilled in the art that the drawings are not necessarily drawn to scale. In the drawings:
fig. 1 is a schematic structural view of a light emitting diode epitaxial wafer prepared in example 1.
Detailed Description
In order that the manner in which the above-recited objects, features and advantages of the present application are obtained will be readily apparent, a more particular description of the invention briefly described above will be rendered by reference to specific details that are set forth in the appended description, which are indicative of but are capable of being practiced in a variety of ways other than those specifically described herein, and which are readily apparent to those of ordinary skill in the art, and which are therefore not limited to the specific embodiments disclosed below.
The present application provides an organomagnesium compound having a structure represented by the following structural formula (1):
For ease of understanding and description, the carbon atoms in structure (1) are numbered, with the carbon atoms in the three methylcyclopentadienyl structures being numbered 1, 2, 3, 4, 5, and 6, with the numbers 1 ', 2', 3 ', 4', 5 ', and 6', and with the numbers 1 ", 2", 3 ", 4", 5 ", and 6", respectively.
The organomagnesium compound represented by the above structural formula (1) has not been reported in the prior art, and as can be seen from the specific structural formula, the organomagnesium compound is composed of two magnesium atoms and three methylcyclopentadienyl groups, which are completely different from the structures of the existing metallocenes, methylmetallocenes, ethylmetallocenes, or the like. Specifically, the core part of the structural formula of the organic magnesium compound is formed by combining two magnesium atoms and three cyclopentadiene groups, wherein the two cyclopentadiene groups are directly connected and are respectively connected with one cyclopentadiene group through one magnesium atom; in the prior art, the organomagnesium compound such as methyl metallocene magnesium or ethyl metallocene magnesium adds substituent groups such as methyl and ethyl on the metallocene ring on the basis of keeping the core structure of the metallocene magnesium.
The organic magnesium compound is liquid in a working state, has stable high saturated vapor pressure, and is very suitable for being used as a magnesium source dopant for semiconductor doping; in the magnesium source process, the magnesium component is uniformly distributed, so that the epitaxy uniformity and the production process stability are improved, and the method is suitable for large-size substrate epitaxy; on the other hand, the vapor pressure is very stable in the last stage of the use of the magnesium source, so that the use efficiency and the mobility of gallium production are improved, the production cost is reduced, and the method is suitable for large-scale mass production.
The organomagnesium compound represented by structural formula (1) is prepared as follows:
in an anhydrous oxygen-free glove box, 98 g of high-purity magnesium chips are added into a cylindrical quartz synthesis column with a heating wire, the magnesium chips are supported by a baffle in the synthesis column, and the synthesis column is vertically arranged; a 500 ml constant pressure funnel with a cock is connected above the synthesis column, 500 ml of methyl cyclopentadiene monomer is added in the funnel, and the upper opening of the funnel is connected with an argon steel cylinder; a 2000 ml two-mouth flask is connected below the synthesis column, the residual interface of the flask is connected with a snake-shaped condenser, the cooling liquid is set to be 32 ℃, and the upper port of the condenser is connected with a tail gas absorption device; purging the synthesis device with 5L/min of gas flow to replace nitrogen in the synthesis device, wherein the purging time is 30 min, and after purging is finished, adjusting the gas flow to a bubbler to bubble at a constant speed of 1 bubble per second; controlling the voltage of the heating wire by using a voltage regulator, controlling the temperature of the synthesis column to be about 540 ℃ by using a thermocouple, and stabilizing for 30 min; dripping methyl cyclopentadiene monomer at the speed of 1 drop per second, receiving mist in a bottle, cooling the mist into the bottle through a condenser, and finally obtaining 360 g of reaction liquid; concentrating the reaction solution by a simple distillation device at normal pressure to obtain a crude product concentrated solution; building a vacuum rectification device, putting the crude product concentrated solution into a kettle of the rectification device, purifying the crude product in a vacuum rectification mode under the absolute pressure of 0.1 kilopascal, and collecting fractions with the top temperature of 58-63 ℃ to obtain a liquid organic magnesium compound with the yield of about 60%.
The liquid organic magnesium compound has melting point of 28-31 deg.C, and is colorless and transparent.
Warp beam1H NMR (hydrogen nuclear magnetic resonance) detection shows that the obtained liquid organic magnesium compound does not contain organic impurities, and the organic content of the obtained liquid organic magnesium compound is more than 99.9 percent.
Through the total element detection of ICP-OES (inductively coupled plasma emission spectrometer), the content of all inorganic impurities in the liquid organic magnesium compound is less than 1 ppm, wherein the content of silicon impurities is about 0.2 ppm, the purity of the liquid organic magnesium compound is as high as 99.9999%, and the raw material use requirement of the semiconductor industry is met.
The specific structure of the liquid organomagnesium compound can be confirmed by characterizing the liquid organomagnesium compound.
The specific means for characterizing the liquid organomagnesium compound includes1H NMR (hydrogen nuclear magnetic resonance), COSY-NMR (two-dimensional correlation spectrum of nuclear magnetic resonance), HSQC-NMR (heteronuclear single quantum correlation spectrum of nuclear magnetic resonance), HMBC (heteronuclear hydrocarbon correlation spectrum),13C-NMR (nuclear magnetic resonance carbon spectrum) and GC-MS (gas chromatography-mass spectrometry).
The characterization results were as follows:
1as a result of the characterization by H NMR,1H NMR (400 MHz， C6D6)： δ = 6.06 (1 H， s， H2)， 5.93 (4 H， dd， J = 2.69 Hz， H2’， H2’’， H4’， H4’’)， 5.80 (4 H， dd， J = 2.70 Hz， H4， H5， H5’， H5’’)， 2.07 (9 H， s， H6， H6’， H6’’)；
COSY-NMR was characterized by a 2.07 ppm peak (H6, H6 ', H6' ') coupled to a 5.80 ppm peak (H4, H5, H5', H5 ''), and a 5.80 ppm peak coupled to a 5.93 ppm peak (H2 ', H2' ', H4', H4 '');
characterization of HSQC-NMR showed that the 2.07 ppm peak was coupled to the 13.48 ppm peak (C6, C6 ', C6 "), the 5.80 ppm peak (H4, H5, H5 ', H5") was coupled to the 106.7 ppm peak (C4, C5, C5 ', C5 "), the 5.93 ppm peak (H2 ', H2", H4 ', H4 ") was coupled to the 105.9 ppm peak (C2 ', C2", C4 ', C4 "), and the 6.06 ppm peak (H2) was coupled to the 107.1 ppm peak (C2);
characterization of HMBC showed that the 5.80 ppm peak (H4, H5, H5 ', H5 ") and the 5.93 ppm peak (H2', H2 ', H4', H4") were both remotely coupled to the 119.1 ppm peak (C1, C1 ', C2 ", C3', C3") and the 118.9 ppm peak (C3);
13as a result of the characterization by C-NMR,13C NMR (125 MHz， C6D6)： δ = 119.1 (C1， C1’， C2’’， C3’， C3’’)， 118.9 (C3)， 107.1 (C2)， 106.7 (C4， C5， C5’， C5’’)， 105.9 (C2’， C2’’， C4’， C4’’)， 13.48 (C6， C6’， C6’’)；
characterization of GC-MS, GC-MS (EI)+)： 281.2 [M - H]+Calculated value C18H17Mg2: 281.1, respectively; % Mg (ICP-OES): 17.20%, calculated: 17.20 percent.
Based on the above characterization analysis of the liquid organomagnesium compound, it can be confirmed that the liquid organomagnesium compound has a structure represented by structural formula (1).
The following are examples of the use of organomagnesium compounds represented by the structural formula (1):
example 1
Preparing an epitaxial wafer of a light emitting diode using an organomagnesium compound represented by structural formula (1) as a dopant:
1) placing a sapphire substrate on a carrying disc in an MOCVD reaction chamber, and growing a buffer layer with the thickness of 25 nm at the temperature of 540 ℃ and the growth pressure of 300 torr, wherein the buffer layer is a low-temperature GaN buffer layer, the Ga source required by growth is TMG (trimethyl gallium), and the growth atmosphere is H2An atmosphere;
2) growing an unintended doped nitride layer of 2.5 μm on the buffer layer at 1080 deg.C and 200 torr pressure, wherein the unintended doped nitride layer is an unintended doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
3) growing an N-type nitride layer with the thickness of 2.5 μm on the unintentionally doped nitride layer at 1060 deg.C and the growth pressure of 200 torr, wherein the N-type nitride layer is an N-GaN layer, and the doping concentration of Si is 8 × 1018Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
4) in thatGrowing a nitride light emitting layer on the N-type nitride layer under the conditions of 750 ℃ of temperature and 250 torr of growth pressure, wherein the nitride light emitting layer is a periodically and repeatedly grown 9 pairs of InGaN/GaN quantum well light emitting layers, the thickness of an InGaN well layer is 3 nm, the growth temperature is 750 ℃, and the growth atmosphere is switched to N2Atmosphere, the thickness of the GaN barrier layer is 11 nm, the growth temperature is 810 ℃, and the growth atmosphere is switched to H2Atmosphere, wherein a Ga source required by growth is TEG (triethyl gallium), and an In source is TMIn (trimethyl indium);
5) growing a 40 nm P-type nitride insertion layer on the N-type nitride layer at 770 deg.C and 200 torr growth pressure, wherein the P-type nitride insertion layer is a P-GaN layer, the organic magnesium compound shown in formula (1) is used as dopant, and the doping concentration of magnesium is 5 × 1019Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is N2An atmosphere.
6) Growing a 25 nm P-type nitride electron blocking layer on the P-type nitride insertion layer at 970 ℃ and under the growth pressure of 200 torr, wherein the P-type nitride electron blocking layer is a P-type AlGaN layer, an organic magnesium compound shown in a structural formula (1) is used as a dopant, and the doping concentration of magnesium is 1.5 multiplied by 1020Per cm3The Ga source required by growth is TMG source, Al source is TMAl (trimethylaluminum), and the growth atmosphere is N2An atmosphere.
7) Growing a 50 nm P-type nitride hole layer on the P-type nitride electron blocking layer at 970 ℃ and under the growth pressure of 200 torr, wherein the P-type nitride hole layer is a P-type GaN layer, an organic magnesium compound shown in a structural formula (1) is used as a dopant, and the doping concentration of magnesium is 5 multiplied by 1019Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
8) Growing a 3 nm P-type nitride contact layer on the P-type nitride hole layer at 790 deg.C and 200 torr growth pressure, wherein the P-type nitride contact layer is a P-type InGaN layer, the organic magnesium compound shown in formula (1) is used as dopant, and the magnesium doping concentration is 2 × 1020Per cm3The Ga source required by growth is TMG source, and the growth atmosphere is cutChange to N2An atmosphere.
Fig. 1 is a schematic structural diagram of a light emitting diode epitaxial wafer prepared in example 1, which sequentially includes, from bottom to top, a sapphire substrate 1, a low-temperature GaN buffer layer 2, an unintentionally doped GaN layer 3, an N-GaN layer 4, an InGaN/GaN quantum well light emitting layer 5, and a multiple quantum well structure 6, where the multiple quantum well structure 6 includes: a P-type nitride insertion layer 61, a P-type nitride electron blocking layer 62, a P-type nitride hole layer 63, and a P-type nitride contact layer 64.
Comparative example 1
Preparing an epitaxial wafer of the light-emitting diode by using the magnesium metallocene as a dopant:
the epitaxial wafer of the light emitting diode in comparative example 1 was prepared in substantially the same manner as in example 1, except that solid magnesium metallocene was used as the magnesium source dopant, and the preparation process was as follows:
1) placing a sapphire substrate on a carrying disc in an MOCVD reaction chamber, and growing a buffer layer with the thickness of 25 nm at the temperature of 540 ℃ and the growth pressure of 300 torr, wherein the buffer layer is a low-temperature GaN buffer layer, the Ga source required by growth is TMG (trimethyl gallium), and the growth atmosphere is H2An atmosphere;
2) growing an unintended doped nitride layer of 2.5 μm on the buffer layer at 1080 deg.C and 200 torr pressure, wherein the unintended doped nitride layer is an unintended doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
3) growing an N-type nitride layer with the thickness of 2.5 μm on the unintentionally doped nitride layer at 1060 deg.C and the growth pressure of 200 torr, wherein the N-type nitride layer is an N-GaN layer, and the doping concentration of Si is 8 × 1018Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
4) growing a nitride light emitting layer on the N-type nitride layer under the conditions of 750 ℃ of temperature and 250 torr of growth pressure, wherein the nitride light emitting layer is a periodically and repeatedly grown 9 pairs of InGaN/GaN quantum well light emitting layers, the thickness of an InGaN well layer is 3 nm, the growth temperature is 750 ℃, and the growth atmosphere is switched to N2Atmosphere, thickness of GaN barrier layer11 nm, the growth temperature is 810 ℃, and the growth atmosphere is switched to H2Atmosphere, wherein a Ga source required by growth is TEG (triethyl gallium), and an In source is TMIn (trimethyl indium);
5) growing a 40 nm P-type nitride insertion layer on the N-type nitride layer at 770 deg.C and 200 torr of growth pressure, wherein the P-type nitride insertion layer is a P-GaN layer, magnesium is used as dopant, and the doping concentration of magnesium is 5 × 1019Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is N2An atmosphere.
6) Growing a 25 nm P-type nitride electron blocking layer on the P-type nitride insertion layer at 970 ℃ and under the growth pressure of 200 torr, wherein the P-type nitride electron blocking layer is a P-type AlGaN layer, the magnesium metallocene is used as a dopant, and the doping concentration of the magnesium is 1.5 multiplied by 1020Per cm3The Ga source required by growth is TMG source, Al source is TMAl (trimethylaluminum), and the growth atmosphere is N2An atmosphere.
7) Growing a 50 nm P-type nitride hole layer on the P-type nitride electron blocking layer at 970 ℃ and under the growth pressure of 200 torr, wherein the P-type nitride hole layer is a P-type GaN layer, the magnesium metallocene is used as a dopant, and the doping concentration of the magnesium is 5 multiplied by 1019Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
8) Growing a 3 nm P-type nitride contact layer on the P-type nitride hole layer at 790 deg.C and 200 torr growth pressure, wherein the P-type nitride contact layer is a P-type InGaN layer, and magnesium is used as dopant with a doping concentration of 2 × 1020Per cm3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to N2An atmosphere.
The luminance of the outer ring of the light emitting diode for preparing the epitaxial wafer based on the different magnesium source dopants in the example 1 and the comparative example 1 was measured, and it was found that the luminance curves of the two were substantially consistent in the light emitting wavelength range between 450-470 nm, the maximum luminance was about 455 nm, and the maximum luminance was about 300 mW, thereby proving that the doping effects of the devices prepared by using the organic magnesium compound represented by the structural formula (1) and the magnesium metallocene as dopants were equivalent.
Compared with the condition that the brightness of the device is kept equivalent when the magnesium metallocene is used as a doping agent, the organic magnesium compound shown in the structural formula (1) is liquid in a working state, has more stable high saturated vapor pressure, has uniform distribution of magnesium components, and has more stable vapor pressure at the end stage of the use of a magnesium source, so that the use efficiency and the gallium production momentum are improved, the production cost is reduced, the process requirement is lower, and the device is suitable for large-scale mass production.
In addition, the organic magnesium compound shown in the structural formula (1) is not only applied to the epitaxial layer of the light emitting diode, but also other electronic devices such as a transistor, a laser, a detector or a solar cell relate to magnesium-doped epitaxial layers, and the magnesium doping of the epitaxial layers can also adopt the organic magnesium compound as a dopant in the application.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the present application have been illustrated and described in detail herein, many other variations and modifications consistent with the principles of the application may be ascertained or derived directly from the disclosure herein without departing from the spirit and scope of the application. Accordingly, the scope of the present application should be understood and interpreted to cover all such other variations or modifications.
Claims (5)
1. An organomagnesium compound characterized by having a structure represented by the following structural formula (1):
2. An electronic device comprising an epitaxial layer comprising a doping of magnesium atoms, wherein said magnesium atoms are provided by the organomagnesium compound of claim 1.
3. The electronic device of claim 2, wherein the epitaxial layer is AlaInbGa1-a-bAnd N layers, wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, a + b is more than or equal to 0 and less than or equal to 1, and the values of a and b are constant, linear or nonlinear.
4. The electronic device of claim 3, wherein the Al isaInbGa1-a-bThe doping concentration of magnesium atoms in the N layer is 1 × 1018Per cm3To 5X 1020Per cm3In the meantime.
5. The electronic device of claim 2, wherein the electronic device is a light emitting diode, a transistor, a laser, a detector, or a solar cell.
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| CN106207200A (en) * | 2016-08-19 | 2016-12-07 | 北京大学 | The nitride microorganism fuel cell cathode of a kind of hetero-epitaxy and battery and method |
| CN112004959A (en) * | 2018-04-20 | 2020-11-27 | 株式会社Adeka | Raw material for forming thin film for atomic layer deposition method and method for producing thin film |
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| CN1173072C (en) * | 2002-08-26 | 2004-10-27 | 南京大学 | Prepn of solution maghesium source |
| JP2007254408A (en) * | 2006-03-24 | 2007-10-04 | Ube Ind Ltd | High-purity bis(cyclopentadienyl)magnesium and method for producing the same |
| CN113461717B (en) * | 2021-09-06 | 2021-11-23 | 江苏南大光电材料股份有限公司 | Organomagnesium compound and electronic device |
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| CN106207200A (en) * | 2016-08-19 | 2016-12-07 | 北京大学 | The nitride microorganism fuel cell cathode of a kind of hetero-epitaxy and battery and method |
| CN112004959A (en) * | 2018-04-20 | 2020-11-27 | 株式会社Adeka | Raw material for forming thin film for atomic layer deposition method and method for producing thin film |
Non-Patent Citations (3)
| Title |
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| Bis(fulvalene)dimetal Complexes Revisited: Synthesis and Properties of [M2(2,2",4,4"-(Me3C)4C10H4)2] (M =Mg, Fe, Mn);Walter, Marc D. et al;《Organometallics》;20191231;第38卷;第3680-3687页 * |
| Construction of double- and triple-decker sandwich compounds from half-sandwich compounds: a theoretical assessment;Zhang, Mei et al;《Journal of Molecular Modeling》;20151231;第21卷;第1-8页 * |
| 夹心多核茂合物Cp2Mgn结构和储氢性能的第一性原理研究;安博等;《人工晶体学报》;20151231;第44卷;第1398-1403页 * |
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