CN103866390A - Method for doping zinc into gallium phosphide polycrystal - Google Patents
Method for doping zinc into gallium phosphide polycrystal Download PDFInfo
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- CN103866390A CN103866390A CN201210535514.8A CN201210535514A CN103866390A CN 103866390 A CN103866390 A CN 103866390A CN 201210535514 A CN201210535514 A CN 201210535514A CN 103866390 A CN103866390 A CN 103866390A
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Abstract
A method for doping zinc into gallium phosphide polycrystal means that zinc impurity is doped during synthesis of gallium phosphide polycrystal. The method comprises: putting Zinc in a graphite pipe loading gallium, enveloping the graphite pipe with a quartz reaction tube, putting in a high-pressure zoned melting synthetic furnace, raising the temperature of the gallium end, raising the temperature of the phosphorus end, when the temperature reaches a preset temperature, starting to synthesize, moving the quartz reaction tube, raising the temperature of the phosphorus end, and measuring the impurity concentration at the end and the tail of the synthesized zinc-doped gallium phosphide polycrystal. The advantages comprise that the method can be directly applied to pulling of zinc doped gallium phosphide monocrystal, and impurity zinc does not need additionally adding when the monocrystal is pulled, therefore, zinc volatilization is reduced in the monocrystal pulling process, observation on monocrystal pulling process is facilitated, monocrystal yield is facilitated to be improved, and also the doping concentration of the monocrystal is well controlled.
Description
Technical field
The present invention relates to adulterating method in a kind of compound semiconductor crystal, specifically, relate to mix zinc method in a kind of gallium phosphide polycrystal body.
Background technology
GaP crystal divides polycrystalline and monocrystalline.Monocrystal of gallium phosphide material is the main substrate of preparing LED, can be used for manufacturing red, yellow, and green look photodiode.Gallium phosphide polycrystal also can be used as the source material of preparation LED simultaneously.When as source material, use is non-doping gallium phosphide polycrystal conventionally, and gallium phosphide non-doped crystal is at room temperature transparent salmon solid.And while being substrate material, mostly be gallium phosphide N-type or P type monocrystalline.Not yet make at present the semi-insulating monocrystal of gallium phosphide of non-doping, obtaining semi-insulating monocrystal of gallium phosphide can only be as other III-V group iii v compound semiconductor material, by introduce deep-level impurity, as mix in the elements such as Cr, Fe, O one or both and become semi insulating material.Present industrial N-type monocrystal of gallium phosphide conventionally by mixing S, Si, Te impurity makes.And industry preparation P type monocrystal of gallium phosphide is to obtain by mixing Zn impurity.
Mix Zn monocrystal of gallium phosphide and prepare yellow, yellow-green colour LED for LPE method or VPE method extension.Modern semiconductors industrial production monocrystal of gallium phosphide is all in high pressure synthetic furnace, adopt the synthetic gallium phosphide polycrystal of directional solidification processes, after suitably processing, pack the monocrystalline in high pressure single crystal growing furnace high pressure LEC method growth <111>, <115> crystal orientation into.Mix Zn monocrystal of gallium phosphide for obtaining, normally doping agent Zn is put into quartz crucible with non-mixing together with gallium phosphide polycrystal, then put into boron oxide insulating covering agent in the above, pack growing single-crystal in high pressure single crystal growing furnace into.Because Zn saturated vapor pressure of (1467 DEG C) when the gallium phosphide fusing point approaches 5MPa, therefore in single crystal growth process, constantly there is Zn to evaporate from gallium phosphide melt, make the blackening of boron oxide insulating covering agent, impact is observed, have a strong impact on seeding and with pontoon control crystal diameter, make monocrystalline yield rate step-down.Meanwhile, due to the volatilization of Zn, add Zn very low effective segregation coefficient in gallium phosphide, make the doping content of monocrystalline be difficult to control.
Summary of the invention
The object of the present invention is to provide in a kind of gallium phosphide polycrystal body and mix zinc method, adopt the method to can be good at controlled doping concentration, while adopting the synthetic polycrystalline of this method to carry out crystal-pulling, being unlikely to again has too many zinc volatilization, improves monocrystalline yield rate.
In order to achieve the above object, the present invention has adopted following technical scheme:
In this gallium phosphide polycrystal body, mix zinc method, it is that one is mixed zinc impurity in gallium phosphide polycrystal building-up process, wherein, zinc is put into the carbon tube of dress gallium, carbon tube is enclosed in crystal reaction tube, put into high pressure area and fuse into stove, the intensification of gallium end, phosphorus end are heated up, after arrival temperature, start to synthesize mobile crystal reaction tube, phosphorus end is heated up, test the synthetic zinc gallium phosphide polycrystal impurity concentration end to end of mixing.
It comprises following concrete steps:
1. 1～8 gram of zinc is placed in the carbon tube that packs gallium into, is placed on 1/2～2/3 place from carbon tube head;
2. carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove, zone length is set as 8～13cm;
3. gallium end temperature is risen to 1450～1500 DEG C, phosphorus end temperature is warming up to 520～540 DEG C and starts to synthesize;
4. move crystal reaction tube with the speed of 7～8 lis ms/h, with the temperature rise rate of 30～40 DEG C/h, phosphorus end is heated up, complete building-up process simultaneously;
5. by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end.The gallium phosphide polycrystal doping content obtaining is not less than 2 × 10
18cm
-3.
It is known equipment that high pressure area fuses into stove,
The melting zone of suitable width refers to gallium end carbon tube heating zone length.
Advantage of the present invention is:
Owing to adopting high pressure area to fuse into, zinc is placed on to correct position, by controlling phosphorus end temperature, and then control phosphorus vapour pressure, suppress the evaporation of zinc, the melting zone of suitable width can make again zinc more be uniformly distributed in whole gallium phosphide polycrystal ingot.
Adopt the present invention synthetic gallium phosphide polycrystal, can be directly used in to draw and mix zinc monocrystal of gallium phosphide, and add in addition zinc impurities while noting be used in crystal-pulling.Therefore, crystal-pulling process has reduced the volatilization of zinc, is convenient to the observation of crystal pulling process, is conducive to improve monocrystalline yield rate, can control well again the doping content of monocrystalline.
Brief description of the drawings
Fig. 1 is the FB(flow block) of mixing zinc method in a kind of gallium phosphide polycrystal body of the present invention.
Embodiment
In a kind of gallium phosphide polycrystal body of the present invention, mixing zinc method employing equipment is high pressure synthetic furnace.
With specific embodiment, the present invention will be further described below:
Embodiment 1:
1. 1 gram of zinc is placed in the carbon tube that packs gallium into, is placed on 1/2 place from carbon tube head;
2. carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove and add thermal synthesis, zone length is set as 8cm;
3. gallium end temperature is risen to 1470 DEG C, phosphorus end temperature is warming up to 520 DEG C and starts to synthesize;
4. move crystal reaction tube with the speed of 7 lis ms/h, with the temperature rise rate of 30 DEG C/h, phosphorus end is heated up, complete building-up process simultaneously;
5. by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end.The gallium phosphide polycrystal head doping content obtaining is 3.6 × 10
18cm
-3.
Embodiment 2:
1. 3 grams of zinc are placed in the carbon tube that packs gallium into, are placed on 1/2 place from carbon tube head;
2. carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove, zone length is set as 9cm;
3. gallium end temperature is risen to 1480 DEG C, phosphorus end temperature is warming up to 525 DEG C and starts to synthesize;
4. move crystal reaction tube with the speed of 7.5 lis ms/h, with the temperature rise rate of 35 DEG C/h, phosphorus end is heated up, complete building-up process simultaneously;
5. by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end.The gallium phosphide polycrystal head doping content obtaining is 8.4 × 10
18cm
-3.
Embodiment 3:
1. 4 grams of zinc are placed in the carbon tube that packs gallium into, are placed on 5/9 place from carbon tube head;
2. carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove, zone length is set as 10cm;
3. gallium end temperature is risen to 1485 DEG C, phosphorus end temperature is warming up to 530 DEG C and starts to synthesize;
4. move crystal reaction tube with the speed of 7.6 lis ms/h, with the temperature rise rate of 33 DEG C/h, phosphorus end is heated up, complete building-up process simultaneously;
5. by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end.The gallium phosphide polycrystal head doping content obtaining is 1.5 × 10
19cm
-3.
Embodiment 4:
1. 7 grams of zinc are placed in the carbon tube that packs gallium into, are placed on 2/3 place from carbon tube head;
2. carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove, zone length is set as 12cm;
3. gallium end temperature is risen to 1490 DEG C, phosphorus end temperature is warming up to 535 DEG C and starts to synthesize;
4. move crystal reaction tube with the speed of 8 lis ms/h, with the temperature rise rate of 36 DEG C/h, phosphorus end is heated up, complete building-up process simultaneously;
5. by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end.The gallium phosphide polycrystal head doping content obtaining is 2.3 × 10
19cm
-3.
Embodiment 5:
1. 8 grams of zinc are placed in the carbon tube that packs gallium into, are placed on 2/3 place from carbon tube head;
2. carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove, zone length is set as 13cm;
3. gallium end temperature is risen to 1500 DEG C, phosphorus end temperature is warming up to 540 DEG C and starts to synthesize;
4. move crystal reaction tube with the speed of 8 lis ms/h, with the temperature rise rate of 40 DEG C/h, phosphorus end is heated up, complete building-up process simultaneously;
5. by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end.The gallium phosphide polycrystal head doping content obtaining is 3.8 × 10
19cm
-3.
Claims (2)
1. in a gallium phosphide polycrystal body, mix zinc method, it is characterized in that: it is that one is mixed zinc impurity in gallium phosphide polycrystal building-up process, wherein, zinc is put into the carbon tube of dress gallium, carbon tube is enclosed in crystal reaction tube, put into high pressure area and fuse into stove, the intensification of gallium end, phosphorus end are heated up, after arrival temperature, start to synthesize mobile crystal reaction tube, phosphorus end is heated up, test the synthetic zinc gallium phosphide polycrystal impurity concentration end to end of mixing.
2. in a kind of gallium phosphide polycrystal body according to claim 1, mix zinc method, it is characterized in that: comprise the following steps:
1). 1～8 gram of zinc is placed in the carbon tube that packs gallium into, is placed on 1/2～2/3 place from carbon tube head;
2). carbon tube is enclosed in crystal reaction tube, puts into high pressure area and fuse into stove, zone length is set as 8～13cm;
3). gallium end temperature is risen to 1450～1500 DEG C, phosphorus end temperature is warming up to 520～540 DEG C and starts to synthesize;
4). the speed with 7～8 lis ms/h moves crystal reaction tube, with the temperature rise rate of 30～40 DEG C/h, phosphorus end is heated up simultaneously, completes building-up process;
5). by synthetic mixing after the taking-up of zinc gallium phosphide polycrystal, test its impurity concentration end to end, the gallium phosphide polycrystal doping content obtaining is not less than 2 × 10
18cm
-3.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59137400A (en) * | 1983-01-26 | 1984-08-07 | Sumitomo Electric Ind Ltd | P type gallium arsenide single crystal with low dislocation density and its manufacture |
| JPH0354185A (en) * | 1989-07-20 | 1991-03-08 | Asahi Glass Co Ltd | Production of iii-v compound semiconductor single crystal |
| JPH06329492A (en) * | 1993-05-21 | 1994-11-29 | Asahi Glass Co Ltd | Production of gaas compound semiconductor crystal |
| JPH0761917B2 (en) * | 1988-03-09 | 1995-07-05 | 株式会社ジャパンエナジー | InP compound semiconductor polycrystalline synthesis method |
| JP3937700B2 (en) * | 2000-07-26 | 2007-06-27 | 日立電線株式会社 | Method for producing GaAs semiconductor single crystal doped with conductive impurities |
| CN101660207A (en) * | 2008-08-26 | 2010-03-03 | 北京有色金属研究总院 | Method for synthesizing gallium phosphide polycrystal |
| CN102040204A (en) * | 2009-10-16 | 2011-05-04 | 北京有色金属研究总院 | Method for casting ingots by using gallium phosphide polycrystal |
-
2012
- 2012-12-12 CN CN201210535514.8A patent/CN103866390B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59137400A (en) * | 1983-01-26 | 1984-08-07 | Sumitomo Electric Ind Ltd | P type gallium arsenide single crystal with low dislocation density and its manufacture |
| JPH0761917B2 (en) * | 1988-03-09 | 1995-07-05 | 株式会社ジャパンエナジー | InP compound semiconductor polycrystalline synthesis method |
| JPH0354185A (en) * | 1989-07-20 | 1991-03-08 | Asahi Glass Co Ltd | Production of iii-v compound semiconductor single crystal |
| JPH06329492A (en) * | 1993-05-21 | 1994-11-29 | Asahi Glass Co Ltd | Production of gaas compound semiconductor crystal |
| JP3937700B2 (en) * | 2000-07-26 | 2007-06-27 | 日立電線株式会社 | Method for producing GaAs semiconductor single crystal doped with conductive impurities |
| CN101660207A (en) * | 2008-08-26 | 2010-03-03 | 北京有色金属研究总院 | Method for synthesizing gallium phosphide polycrystal |
| CN102040204A (en) * | 2009-10-16 | 2011-05-04 | 北京有色金属研究总院 | Method for casting ingots by using gallium phosphide polycrystal |
Non-Patent Citations (2)
| Title |
|---|
| EISHI KUBOTA,ET AL.: "Electrical and optical properties of Mg, Ca, and Zndoped InP crystals grown by the synthesis, solute diffusion technique", 《JOURNAL OF APPLIED PHYSICS》, vol. 55, 15 May 1984 (1984-05-15) * |
| H. KOI，ET AL.: "The Behaviour of Zinc in Gap Synthesis by the SSD Technique", 《CRYSTAL RES. & TECHNOL》, vol. 17, no. 12, 31 December 1982 (1982-12-31), pages 1501 - 1512 * |
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Effective date of registration: 20220302 Address after: 065201 South Youyan Technology Group Co., Ltd. No.2, Xingdu village, Yanjiao, Sanhe City, Langfang City, Hebei Province Patentee after: GRINM GUOJING ADVANCED MATERIALS Co.,Ltd. Address before: 065001 Langfang hi tech Development Zone, Hebei Province Patentee before: GRINM ELECTRO-OPTIC MATERIALS CO.,LTD. |