CN101311364B

CN101311364B - Process for preparing P-shaped zinc oxide semiconductor bulk material

Info

Publication number: CN101311364B
Application number: CN2008100504506A
Authority: CN
Inventors: 秦杰明; 姚斌; 张吉英; 申德振; 赵东旭; 张振中; 李炳辉
Original assignee: Changchun Institute of Optics Fine Mechanics and Physics of CAS
Current assignee: Changchun Institute of Optics Fine Mechanics and Physics of CAS
Priority date: 2008-03-10
Filing date: 2008-03-10
Publication date: 2010-12-15
Anticipated expiration: 2028-03-10
Also published as: CN101311364A

Abstract

The invention relates to a method for preparing 'p' typed zinc oxide semiconductor body material, The method comprises the following steps: a mixed power body, consisting of ZnO with the molar ratio of 95-99.9 percent and Sb with the molar ratio of 5-0.1 percent, is used as a raw material; the raw material is sintered under a thermal compression under the pressure of 2-5.4 GPa and the temperatureof 1400-1600 DEG C, thus obtaining a 'p' typed ZnO polycrystal body material. The 'p' typed zinc oxide semiconductor body material prepared by the method has a carrier concentration of 1.0*10<13-21>cm<-3>, a resistivity of 1*10<0.01-3>omega.cm, and a mobility of 0.01-13cm<2>.V<-1>.S<-1>. The obtained 'p' typed zinc oxide semiconductor body material has a good crystallization in quality; good repeatability of the preparation; and the body material is suitable for industrialized production; thus high-class new material which is especially applicable to the technical filed of manufacturing optoelectronic device is provided.

Description

The method for preparing p type zinc oxide semiconductor bulk material

Technical field

The present invention relates to prepare the method for P type zinc oxide semiconductor bulk material, particularly a kind of High Temperature High Pressure (HPHT) sintering process prepares the processing method of P type zinc oxide semiconductor bulk material.

Background technology

High Temperature High Pressure (HPHT) technical applications is extensive; be characterized in to make the Solid solution material to reach solute solid solubility in high-density and the increase sosoloid rapidly; even crystalline structure even atom, electronic state are changed; thereby can intercept and capture some characteristic of Solid solution under the high pressure; make it to show at normal temperatures and pressures, give the Solid solution material in common following inaccessible performance of chemical reaction.In recent years, ZnO is in the great development potentiality of photoelectric field and be subjected to people's extensive concern.This has many advantages because of ZnO as a kind of novel II-VI compound semiconductor, as room temperature energy gap big (3.37eV), and exciton bind energy (60meV) and the high (300cm of exciton gain ^-1), be to realize one of the most potential semiconductor material of ultraviolet light photo device.

As intrinsic ZnO (N type) semi-conductor, realize that high density N type mixes than being easier to, common doped with Al, Ga, elements such as In can obtain the ZnO semiconductor material of low-resistance N type conduction, the preparation of p type ZnO is then difficult relatively, is owing to have many intrinsic alms giver's defectives among the ZnO on the one hand, can produce highly self compensation effect as zinc gap (Zni) and oxygen room (Vo); Then be because the solid solubility of being led among the ZnO is very low on the other hand, and acceptor level is dark, is difficult to ionization.In the research that the P type that realizes ZnO changes, inquiring into maximum is V family doped element, and document has also been reported element such as N in the use V family in succession, P, and As, Sb has prepared p type ZnO as doping agent.But the p type ZnO preparation method of report mostly is the employing thin film technique at present, as rf magnetron sputtering, and MBE or the like, and many employing annealing realizes that as the hot activation process P type of ZnO film changes.But, utilize the p type ZnO of method for preparing all to exist the resistivity height, carrier concentration is low, and p type conductive stability is poor, the difficulty that repeatability is bad.These difficulties have become the bottleneck of restriction ZnO researchdevelopment.

High pressure is as except composition, and the 3rd thermodynamics dimension beyond the temperature can change the many physics and the chemical property of material, as: increase the solid solubility of material, change the electronic structure of material, form the novel substance that is difficult to obtain under the normal pressure etc.People are also carrying out number of research projects aspect the P-ZnO body material in recent years, but also do not prepare the method and the product of P-ZnO polycrystal semiconductor bulk material so far.For this reason, we utilize high-pressure high-temperature technology to carry out the preparation work of p type ZnO, in the hope of obtaining high electricity and optical quality, but the p type ZnO of stable performance duplication of production.

Summary of the invention

The objective of the invention is to propose a kind of method of the P of preparation type zinc oxide semiconductor bulk material, to obtain high electricity and optical quality, but the multicrystal semiconductor bulk material of p type ZnO of stable performance duplication of production provides the high-quality novel material of particularly suitable for photoelectric device manufacturing technology field.

The present invention prepares the method for p type zinc oxide semiconductor bulk material, being to be that the mixed powder of 95%～99.9%ZnO and 5%～0.1%Sb is a raw material with molar percentage, is that 2～5.4GPa, temperature are that hot pressed sintering makes p type ZnO polycrystal body material under 1400～1600 ℃ of conditions at pressure.

With the P type ZnO semiconductor bulk material of the inventive method preparation, its carrier concentration is 1.0 * 10 ^13～21Cm ^-3, resistivity is 1 * 10 ^0.01-3Ω .cm, mobility is 0.01～13cm ².V ^-1.S ^-1

The present invention utilizes high temperature and high pressure method to prepare p type ZnO semiconductor bulk material, does not still have bibliographical information at present.The present invention has following characteristics: 1. High Temperature High Pressure not only can make the body material of ZnO:Sb reach high-density rapidly and increase solute Sb solid solubility, even crystalline structure even atom, electronic state are changed, thereby can intercept and capture p-ZnO characteristic under the High Temperature High Pressure, make it to show at normal temperatures and pressures.2. the component that can come the control volume material by accurate control ZnO and Sb molar percentage; The multicrystal semiconductor bulk material crystalline quality of p type ZnO that the inventive method obtained is good; The preparation good reproducibility; Be suitable for suitability for industrialized production.3. selected preparation method is new, has essential difference especially with the p-ZnO method for manufacturing thin film of forefathers' report, particularly the report of p-ZnO:Sb body material is not also seen, simultaneously less than in the 5mol% scope, the adjusting by pressure and temperature realizes that ZnO and Sb are molten mutually arbitrarily to Sb in the component of ZnO.

Embodiment

By the following examples the present invention is further elaborated.

The present invention prepares the method for P type zinc oxide semiconductor bulk material, is to be raw material with powder ZnO and Sb, as production unit, is that 2～5.4GPa, temperature be 1400～1600 ℃ conditions under hot pressed sintering make P-ZnO polycrystal at pressure with six-plane piercer.Its specific practice is: powder ZnO and the Sb uniform mixing that will set the molar percentage component, in the agalmatolite module of packing into behind the pre-molding cavity, this agalmatolite module that ZnO and Sb uniform mixture are housed inserted in the six-plane piercer pressure chamber pressurize, after pressure reaches the operating pressure of setting by electric current with the ZnO in the module and Sb mixture heating up to the working temperature of setting, heat-insulation pressure keeping is 20 minutes under the operating pressure of this setting and temperature, promptly obtains P type ZnO polycrystal semiconductor bulk material after the release cooling and demolding.

By the P type ZnO semiconductor bulk material that present method obtains, the carrier concentration that it is characterized in that this material is 1.0 * 10 ^13～21Cm ^-3, resistivity is 1 * 10 ^0.01-3Ω .cm, mobility is 0.01～13cm ².V ^-1.S ^-1

The p type ZnO body material that the inventive method is prepared has been established basic substance for next step ultraviolet light photo preparation of devices and realization.In addition, high-temperature high-pressure apparatus not only is suitable for scientific research, and it is more suitable for large-scale production.

Set of dispense ratio, operating pressure and the p type ZnO polycrystalline material Effect on Performance of temperature by following examples explanation starting material powder ZnO and Sb to preparing.

Embodiment 1

Under fixed pressure and temperature condition, in ZnO, add Sb (mol%) the preparation p type ZnO body material of different content.

ZnO and Sb powder mix with different molar percentage components are synthesis material, are that 5.4GPa, temperature are under 1600 ℃ of conditions at pressure, sintering 20 minutes.

P-ZnO:Sb body material to the above-mentioned different mol ratio of preparing carries out the X-ray diffraction measurement, the result shows that all samples all has single hexagonal structure, wherein the peak value halfwidth narrower (below 0.2) of main diffraction peak (002) illustrates that its crystalline quality is higher relatively.Adopt EDX and X-ray diffraction to measure calculation result and show, the Zn in the sintered sample, Sb and initial proportioning are identical substantially.Show that by hall effect observation shown in table one (5.4GPa, the electric property of the P-ZnO:Sb of different ratios ZnO:Sb preparation under 1600 ℃ of conditions), along with the increase of Sb content among the ZnO, the resistance of material becomes downtrending, carrier concentration increases.Utilize the present invention, can increase the solid solubility of Sb in ZnO, this explanation utilizes high temperature and high pressure method to prepare semi-conductor p-ZnO:Sb body material (Sb the component of ZnO less than the 5mol% scope in) technology, is existing remarkable advantages aspect the preparation of this material.

Table one

Sample	?ZnO?(mol％)	?Sb?(mol％)	Resistivity/Ω .cm	Carrier concentration/cm ^-3	Mobility/V ^-1.S ^-1	Conduction type
							1	100	0	-	-	-	-
2	99.9	0.1	1123	1.32×10 ¹³	0.01	p
							3	99.5	0.5	112	2.57×10 ¹⁶	0.19	p
4	99	1	7.83	1.57×10 ¹⁹	4.3	p
							5	98	2	0.13	3.91×10 ¹⁹	6.5	p
6	96	4	0.012	8.22×10 ²⁰	13	p
							7	95	5	0.006	4.25×10 ²¹	1.16	p

Embodiment 2

Under fixed pressure and raw material ratio condition, improve semi-conductor P type ZnO body quality of materials by changing sintering temperature.

With molar percentage 95%ZnO and 0.5%Sb uniform mixture is raw material, under 5.4GPa pressure, and respectively under different temperature, sintering 20 minutes.

The ZnO for preparing under the different temperature is mixed Sb body material to be shown by the hall effect measurement, (ZnO: Sb is 0.95: 0.5 (mol) as table two, pressure is 5.4GPa, the electric property of P-ZnO:Sb under the condition of different temperatures) shown in, the body material that obtains below 1100 ℃ is the N type, 1100～1300 ℃ is weak P type, is the p type more than 1300 ℃.At 1400～1600 ℃ of interval body materials that obtain, its carrier concentration is 1 * 10 ^18-21Cm-3, resistivity 23～0.006 Ω .cm, mobility 0.08～1.16cm2.V-1.S-1 illustrates by changing sintering temperature and can improve P type ZnO body quality of materials.

Table two

Sample	Temperature (℃)	Resistivity/Ω .cm	Carrier concentration/cm ^-3	Mobility/V ^-1.S ^-1	Conduction type
						1	1000	117	2.53×10 ¹⁶	0.24	n
2	1300	74	9.21×10 ¹⁷	0.21	Weak p
						3	1400	52	2.57×10 ¹⁸	0.36	p
4	1500	0.83	5.97×10 ²⁰	4.3	p

5

1600

0.006

4.25×10 ²¹

1.16

p

Embodiment 3

Under fixed temperature and raw material ratio condition, improve P type ZnO body quality of materials by changing sintering pressure.

With molar percentage 95%ZnO and 0.5%Sb uniform mixture is raw material, and sintering temperature is 1600 ℃, respectively under different pressures, and sintering 20 minutes.

Adopt different sintering pressures to prepare the p-ZnO:Sb body material of different mass.Show by the hall effect measuring result, (ZnO: Sb is 0.95: 0.5 (mol) as table three, 1600 ℃ of temperature, the electric property of P-ZnO:Sb under the different pressures condition) shown in, rising along with sintering pressure, the p-ZnO:Sb body material sample quality of preparation increases, and electrical parameter also makes moderate progress.Explanation can improve p-ZnO:Sb body quality of materials by changing sintering pressure.

Table three

Sample	Pressure (GPa)	Resistivity/Ω .cm	Carrier concentration/cm ^-3	Mobility/V ^-1.S ^-1	Conduction type
						1	2	872	4.32×10 ¹⁴	0.07	p
2	3.7	557	7.34×10 ¹⁷	0.11	p
						3	4.6	0.18	9.75×10 ¹⁹	0.86	p
4	5.4	0.006	4.25×10 ²¹	1.16	p

Claims

1. method for preparing p type zinc oxide semiconductor bulk material, it is characterized in that, be to be that the mixed powder of 95%～99.9%ZnO and 5%～0.1%Sb is a raw material with molar percentage, in the agalmatolite module cavity of packing into behind this mixed powder pre-molding, in the six-plane piercer pressure chamber, at pressure is that 2～5.4GPa, temperature are heat-insulation pressure keeping 20 minutes under 1400～1600 ℃ of conditions, promptly obtains p type ZnO polycrystal body material.