CN100401602C

CN100401602C - Zinc oxide bluish violet light semiconductor growth using liquid phase epitaxial method

Info

Publication number: CN100401602C
Application number: CNB2003101152588A
Authority: CN
Inventors: 涂朝阳; 吴柏昌; 李坚富; 朱昭捷; 王燕; 游振宇; 黄燕
Original assignee: Fujian Institute of Research on the Structure of Matter of CAS
Current assignee: Fujian Institute of Research on the Structure of Matter of CAS
Priority date: 2003-11-27
Filing date: 2003-11-27
Publication date: 2008-07-09
Anticipated expiration: 2023-11-27
Also published as: CN1622409A

Abstract

The present invention discloses a method for producing a bluish-violet optical ZnO semiconductor by a liquid-phase epitaxial method. The present invention comprises: firstly, selecting a growth system containing a fluxing agent of P2 O5 and producing a p-type ZnO semiconductor monocrystal doped with P<5+> ions by a molten salt method; then, selecting a growth system containing a fluxing agent of Al2 O3 and producing an n-type ZnO semiconductor monocrystal doped with Al<3+> ions on the surface of the p-type ZnO semiconductor monocrystal; processing the n-type ZnO semiconductor monocrystal with a crystal device to prepare a bluish-violet optical ZnO semiconductor device with a p-n junction. The bluish-violet optical ZnO semiconductor monocrystal produced by the method has the advantages of low defect, high integrity, simple growth equipment and cheap expense.

Description

A kind of liquid phase epitaxial method that is used for developing zinc oxide royal purple photosemiconductor

Technical field

The present invention relates to the crystalline material preparation field.The Liquid method that particularly relates to the ZnO royal purple photosemiconductor monocrystalline of a kind of low defective, high integrality.

Background technology

ZnO is the II-VI semiconductor, has direct broad-band gap, band gap E _gBe 3.37ev, the bonded energy of exciton is big, its value is 60ev, can produce ultraviolet light, replace blue laser if make ultraviolet laser, become compact disk of new generation (CD) reader, can be so that CD dish groove be littler, the data of optical disk reserves will enlarge several times, be the focuses of present various countries scientist keen competition.Recently, U.S.'s ballistic missile defense plan tissue (BMDO) has been invested 1,000,000 dollars, allows Cermet company develop the ZnO semiconductor technology.Mainly be the semi-conductive p-n junction technology of development ZnO, the enforcement of this engineering then mainly is to use ZnO bulk crystal growth technology, certainly, also might adopt film growth techniques.

Though it is the semi-conductive energy gap of ZnO is enough big, all very unsuccessful with the trial of this made laser.Though crystal can be induced the photon of emission ultraviolet light, this emission light is very faint, and chief reason is that the defective in the crystal absorbs photon.

Therefore, in order to satisfy the needs of using, requirement is growing large-size, high-quality ZnO crystal in large quantity.Simultaneously, in order to form p-n junction, some ions that need require in the crystal to mix.

At present, ZnO crystal mainly be adopt hydro thermal method (R.A.Laudise, E.D.Kolb, A.J.Caporaso, J.Am.Cream.Soc.47 (1964) 9; T.Sekiguchi, S.Miyashita, K.Obara et al.J.CrystalGrowth 214/215 (2000) 72; ), vapour phase processes (D.C.Look, D.C.Reynolds, J.R.Sizelove et al.Solid State Commun.150 (1998) 399; ), from melt at a slow speed falling temperature method (J.Phys.Chem.64 (1960) 1762 for J.W.Nielsen, E.F.Dearborn; B.M.Wanklyn, J.Crystal Growth7 (1970) 107.) growth.But these methods can only grow the less crystal of size, also can be satisfied with the requirement of application far from.ZnO melts with composition at 1975 ℃, but at high temperature volatility is very big for it, and therefore the Czochralski method as the growing large-size crystal can not be applicable to ZnO crystal.Yet the employing molten-salt growth, not only expense is cheap, and equipment is simple, crystal that can growing large-size, but also can reduce growth temperature, reduce the volatilization of ZnO, simultaneously, can also select the flux of suitable component, make and mix into required suitable ion in the crystal.Certainly, adopting an outstanding feature of molten salt growth method is that growth rate is slower, yet this but helps the ordered arrangement of ion in crystal, reduces the defective of position vacancy in the crystal.And, adopt the liquid phase epitaxial method growth based on the growing principle of molten salt growth method, just can prepare ZnO royal purple luminescent semiconductor device with complete p-n junction.

Summary of the invention the objective of the invention is to adopt the ZnO royal purple photosemiconductor monocrystalline of the low defective of liquid phase epitaxial method growth, high integrality.Based on the growing principle of molten salt growth method, select to contain P respectively ₂O ₅And Al ₂O ₃The growth system of flux adopts liquid phase epitaxial method to piece together roped party dress ZnO-p and ZnO-n semiconductor monocrystal, and preparation has the high-quality ZnO royal purple luminescent semiconductor device of low defective, high integrality and complete p-n junction.

Realize that the object of the invention technical scheme is: at first select to contain P ₂O ₅The growth system of flux adopts molten-salt growth to go out to be doped with P ⁵⁺The ZnO-p N-type semiconductor N monocrystalline of ion; Select to contain Al then ₂O ₃The growth system of flux adopts liquid phase epitaxial method, grows at ZnO-p N-type semiconductor N single-crystal surface and is doped with Al ³⁺The ZnO-n N-type semiconductor N monocrystalline of ion, crystal-cut, make the ZnO-p N-type semiconductor N monocrystalline and the ZnO-n semiconductor monocrystal size at p-n junction two ends equate,, can prepare ZnO royal purple luminescent semiconductor device with p-n junction in two end face polishings perpendicular to p-n junction.

Growth course is as follows: after the raw material weighing, pack into after evenly in the platinum alloy crucible of Φ 70mm * 70mm with the agate mortar ground and mixed, 1100 ℃ of following constant temperature 24 hours, lower the temperature with the rate of temperature fall of 5 ℃/d then, during growth ending, handle isolation of crystalline with deionized water.Adopt then with the crystal of gained as seed crystal further growth megacryst: after the raw material fusing, measure the saturation temperature of melt with attempting the seed crystal method, more than saturation about 30 ℃ with seed crystal in melt, after half an hour melt is reduced to saturation temperature, beginning is with the speed cooling of 2-3 ℃/d, and the seed crystal slewing rate is 4.5-9rpm, grow after 15-20 days, crystal is lifted from melt liquid level, then with the near room temperature of the speed of 30 ℃/h

Embodiment

Directly adopt the P of 34mol% ₂O ₅As flux.At first adopt the slowly spontaneous seed crystal preferably that grows of cooling, adopt the top-seeded solution growth grow doping that P is arranged then ⁵⁺The ZnO-p N-type semiconductor N monocrystalline of ion.Raw materials used is the ZnO and the NH of high-purity (greater than 4N) ₄H ₂PO ₄, NH wherein ₄H ₂PO ₄To form P after the heating ₂O ₅,

That is: 2NH ₄H ₂PO ₄→ 2NH ₃↑+3H ₂O ↑+P ₂O ₅

After the raw material weighing, pack into after evenly in the platinum alloy crucible of Φ 70mm * 70mm,, lower the temperature with the rate of temperature fall of 5 ℃/d then, during growth ending, handle isolation of crystalline with deionized water 1100 ℃ of following constant temperature 24 hours with the agate mortar ground and mixed.Adopt then with the crystal of gained as seed crystal further growth megacryst: after the raw material fusing, measure the saturation temperature of melt with attempting the seed crystal method, more than saturation about 300 ℃ with seed crystal in melt, after half an hour melt is reduced to saturation temperature, beginning is with the speed cooling of 3 ℃/d, and the seed crystal slewing rate is 9rpm, grow after 20 days, crystal is lifted from melt liquid level,, can obtain ZnO-p N-type semiconductor N monocrystalline then with the near room temperature of the speed of 30 ℃/h.

Then, ZnO-p N-type semiconductor N monocrystalline is carried out orientation, the direction of a crystal main shaft of selection is carried out optical polish processing, and is standby, adopts the B of 65mol% then ₂O ₃The Al of+10mol% ₂O ₃As flux.Raw materials used is the ZnO and the Al of high-purity (greater than 4N) ₂O ₃, H ₃BO ₃After the raw material weighing, pack into after evenly in the platinum alloy crucible of Φ 70mm * 70mm with the agate mortar ground and mixed, after the raw material fusing, measure the saturation temperature of melt with attempting the seed crystal method, under saturation temperature with the ZnO-p N-type semiconductor N single-crystal surface that processes in melt, beginning is with the speed cooling of 3 ℃/d, the seed crystal slewing rate is 8rpm, grow after 20 days, crystal is lifted from melt liquid level, then with the near room temperature of the speed of 30 ℃/h.Crystal-cut, make the ZnO-p N-type semiconductor N monocrystalline at p-n junction two ends and ZnO-n N-type semiconductor N monocrystalline size equate, in two end face polishings, can prepare ZnO royal purple luminescent semiconductor device with p-n junction perpendicular to p-n junction.

Claims

1. liquid phase epitaxial method that is used for developing zinc oxide royal purple photosemiconductor, this method comprise the growth of ZnO-p N-type semiconductor N monocrystalline and epitaxial growth of ZnO-n N-type semiconductor N monocrystalline and to three parts of crystal processing on ZnO-p N-type semiconductor N monocrystalline:

(1) with P ₂O ₅As flux, adopt molten-salt growth to go out ZnO-p N-type semiconductor N monocrystalline;

(2) with Al ₂O ₃As flux, adopt liquid phase epitaxial method, grow at ZnO-p N-type semiconductor N single-crystal surface and be doped with Al ³⁺The ZnO-n N-type semiconductor N monocrystalline of ion;

(3) crystal that last growth is finished is processed, make ZnO-p N-type semiconductor N monocrystalline and the ZnO-n N-type semiconductor N monocrystalline size in aforementioned (2) in aforementioned (1) at p-n junction two ends equate, in two end face polishings, can prepare ZnO royal purple photosemiconductor with p-n junction perpendicular to p-n junction.