CN100487909C - Heterogeneous p-n nano-line array, its production and use - Google Patents
Heterogeneous p-n nano-line array, its production and use Download PDFInfo
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- CN100487909C CN100487909C CNB2007100273530A CN200710027353A CN100487909C CN 100487909 C CN100487909 C CN 100487909C CN B2007100273530 A CNB2007100273530 A CN B2007100273530A CN 200710027353 A CN200710027353 A CN 200710027353A CN 100487909 C CN100487909 C CN 100487909C
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Abstract
The invention is concerned with heterogeneity p-n junction nanometer line array using laser pulse depositing process under high temperature and voltage and its production. Each nanometer line of the array is made of two parts, n type semiconductor material nanometer line and another p type nanometer line with accordant diameter. The two parts have same length and diameter to form p-n junction and a p-n junction space charge area on the surface. This invention shows the application about heterogeneity p-n junction nanometer line array in semiconductor electronic devices field, such as diode, dynatron, and so on. This invention has simple process and low require to temperature and vacuum, and the used laser is long wave to short reaction time. The speed of depositing process is quick and the influence from other outside factors is small to satisfy the strict chemistry match for producing on scale.
Description
Technical field
The invention belongs to technical field of semiconductors, the preparation method of particularly a kind of heterogeneous p-n nano-line array and this heterogeneous p-n nano-line array thereof and application.
Background technology
Since nineteen forty-seven, U.S. Bell Laboratory U.S. Bell Laboratory has been invented the semiconductor contact transistor, thereby has started the human silicon civilization, just with the closely-related epoch of semiconductor.Between short decades, semiconductor industry has obtained sizable development, and semiconductor produces the life that has also changed people, no matter is civilian or military aspect, exists semiconductor device everywhere.In today of information age, computer has entered into huge numbers of families, and present electronic computer technology is based on large scale integrated circuit, more and more higher for semi-conductive requirement in integrated circuit, semiconductor plays immeasurable effect in our daily life and modern military fighting technique.Except computer, in numerous electronic products, Source Music, display, stop-lights etc. all are based on semiconductor components and devices.Semi-conductive latest development just is being deep into each corner of our daily life.Industrial quarters and scientific research personnel still are devoted to the development and the research of following electronics and optoelectronics industry at present on the basis of semi-conducting material.Semiconductor components and devices mainly comprises two parts: diode and triode (transistor), common semiconductor components and devices comprises the electric capacity in the integrated circuit, switching diode, photodetector, light-emitting diode, semiconductor transistor or the like.Along with the sustainable development of electronics and optoelectronics industry, diode and triode and be widely used by the semiconductor components and devices that both form.And p-n junction is the basis that constitutes above classes of semiconductors device, is the core that constitutes semiconductor device.The base unit of diode is exactly a p-n junction, triode also by two back to p-n junction form, thereby p-n junction plays a very important role on electronics industry.
Along with the continuous development of electronic device, the updating of performance, corresponding with it various electronic devices and components are also constantly improved and are improved.Present various devices all begin to the miniaturization development, and the performance of device is also continued to optimize simultaneously, need assemble more transistor in an element, and for the also more and more miniaturization of requirement of the base unit p-n junction in the transistor.Along with in recent decades, the rise of nanoscale science and technology and development, people have had deep understanding for the preparation and the performance of material on nanoscale, and the thin-film material from the three-dimensional material to the two dimension causes the monodimension nanometer material of researcher's interest more till now.The p-n junction of electronic component is used to such an extent that be the film p-n junction the most widely at present, and at present, people have utilized thin film technique, successfully prepare various p-n junction films, and are applied to semiconductor device.But, film is because its interfacial area is bigger, p-n junction knot face performance is affected easily, the I-V characteristic of corresponding p-n junction, also can decrease by performances such as the diode of its assembling and transistorized life-spans, this also is the difficult point of the maximum that faced of current thin film p-n junction, and growth for Thin Film to equipment requirements than higher, as vacuum degree etc., be difficult in industrial a large amount of preparation that obtains like this.And the development of monodimension nanometer material has opened up a new direction for the preparation of p-n junction.At present, people have prepared various one-dimensional nano structures, as nano wire, and nanometer rods, nanotube etc., and studied their performance, one-dimensional material shows a lot of materials not available performance under other yardsticks because of its dimensional effect.Single nanostructure of planting material is mainly paid attention in research in the past, people begin to attempt preparing heterojunction on one-dimensional nano structure now, as superlattice, p-n junction etc., but these are ground zero, the p-n junction aspect, and people mainly utilize film to form p-n junction with combining of nano wire, p-n junction on the solid wire, rarely have report at present, and heterogeneous p-n aspect on the solid wire is not reported also at present.The nano-structural interfaces of one dimension p-n junction is less, has reduced p-n junction interface loss in the course of the work, the stress influence that also can reduce in the thin film growth process to be brought, and also one-dimensional nano structure is more flexible, the easier assembling of carrying out device.This structure is expected to be widely used in semiconductor industry in the future.
At present, developing many methods aspect the preparation of one-dimensional nano structure, yet, because microcosmic and complexity that nano material itself is possessed, and it is in the not available character of a lot of macroscopic material of possessing of nanoscale scope, thereby the preparation of nanostructure becomes a difficult point in the nanometer technology.The preparation of nanostructure mainly is the wish according to people, utilizes the method for physics or chemistry, and the artificially is assembled nano material, arranged and constitutes the process of one dimension, two and three dimensions nanostructure system on nanoscale.The preparation of nanostructure has obtained some achievements in many aspects, but because the restriction of appointed condition, and extensive, high efficiency, low cost method still realize far away, still in updating.In the preparation of the p-n junction of film, the preparation of film is very high for the requirement of external environment, and this has also improved the industrialization cost greatly.And the preparation aspect of one-dimensional material, be used for existing p-n junction preparation mainly be to use chemical method, as chemical vapour deposition (CVD), the metal vapour phase epitaxy, template etc., but a lot of uncontrollable factors are arranged in the chemical method, and particularly aspect the preparation doping of p-n junction, and chemical method requires temperature than higher, be difficult to obtain perfect condition, thereby can't control the growth of p-n junction well, it is even to be difficult to grow doping, well behaved p-n junction.
Pulsed laser deposition is a kind of technology that is widely used in preparing nano material, is mainly used to prepare various films at present, also begins to be applied in single one-dimensional nano structure of planting material prepares.The experiment parameter of pulsed laser deposition is independent adjustable, the advantage of its maximum is in the preparation process of material, make the material of preparation identical stoicheiometry be arranged with reaction source, this is the unique advantage that it has in this structure preparation process with technology of doping of p-n junction, can come the controlled doping amount by the stoicheiometry of control reaction source.Mentioned pulsed laser deposition all is to carry out under the condition of high vacuum or low-pressure gas at present, focus on target material surface by laser beam, make target material surface produce high temperature and fusion, and further produce plasma, plasma directed local expansion under vacuum or gas condition is launched and is deposited and formation film or nano wire etc. on substrate, this method prepares nano material, and fast growth can be applicable to wide variety of materials.Yet this method is very high to the requirement of instrument, and production cost improves, and is unfavorable for industrial applications.
Summary of the invention
In order to solve the weak point that above-mentioned prior art exists, but primary and foremost purpose of the present invention is to provide the heterogeneous p-n nano-line array of simple, the consuming time preparation of industrialization less of a kind of method.
Another object of the present invention is to provide the HTHP pulse laser deposition process that utilizes after improving to carry out the preparation method of above-mentioned heterogeneous p-n nano-line array, this method is in the technology of preparation p-n junction nano wire, the composition of prepared material is consistent with the stoicheiometry of target, each technological parameter is independent adjustable, preparation speed is fast, and nanowire growth is even, but the advantage of large area deposition, not high to equipment requirements, help industrial mass production.The present invention places the target of two kinds of different materials the molybdenum rod of rotation, be positioned over target and substrate in the reacting furnace together, feed specific gas with certain flow, keep certain air pressure, quartz ampoule is heated to certain temperature and keeps this temperature to be prepared process.Regulate laser beam,, the pulsed laser beam of particular energy, frequency be gathered on the target by beam splitting chip and focus lamp, with this pulse laser in different atmosphere respectively to different target as sputter a period of times.Sputter can obtain heterogeneous p-n nano-line array at substrate surface after finishing the nature cooling.
A further object of the present invention is to provide the application of above-mentioned heterogeneous p-n nano-line array.
Purpose of the present invention is achieved through the following technical solutions: a kind of heterogeneous p-n nano-line array, every nano wire is formed by the uniform n N-type semiconductor N of diameter material nano line and the another kind of nanowires of semiconductor material two-section of p type in the described array, the nanowire length of the different semi-conducting materials of two-section equates and diameter evenly equates, both form p-n junction, and the interface forms a p-n junction space charge region; The semi-conducting material that the n type that described n N-type semiconductor N material is zinc oxide (ZnO) or zinc oxide mixes; The semi-conducting material that the p type that the another kind of semi-conducting material of p type is a gallium nitride (GaN) mixes.
The used target of described n N-type semiconductor N material is that purity is that 99.99% zinc oxide (ZnO) ceramic target or the purity of mixing the MgO of 20% (molar percentage) are 99.99% zinc oxide (ZnO) ceramic target, and the used target of the another kind of semi-conducting material of described p type is 99.99% gallium oxide (Ga for the purity of the MgO that mixes 20% (molar percentage)
2O
3) ceramic target.
In order to realize the present invention better, the diameter of described nano wire is 50～500nm, and length does not wait for about 1～50 micron, and diameter and length all can be regulated by regulating technological parameter.
Utilize pulse laser deposition process in the high temperature and high pressure environment to prepare the method for above-mentioned heterogeneous p-n nano-line array, comprise the steps:
Two kinds of different targets (reaction source) are installed in parallel on the molybdenum rod of the electric rotating machine in the reacting furnace, substrate is positioned in a quartz cell or the potsherd, again this quartz cell or potsherd are positioned in the reacting furnace, make quartz cell or potsherd, target place heating furnace, substrate is between target and laser beam sources; With this reacting furnace forvacuum, reach 10
-3～10
-2Behind the Pa, speed with 35～50sccm (per minute standard milliliter) feeds the required gas of any target reaction that carries out laser splash, make in the reacting furnace air pressure reach 1～5Torr (1Torr=1/760 standard atmospheric pressure=133Pa), reacting furnace is heated after 600～1000 ℃ then, regulate laser, make the laser emission laser beam successively by optical beam splitting sheet and focus lamp, see through the side of substrate vertical focusing to target, side at target produces the plasma plume body, and target was carried out laser splash 20～60 minutes; Change gas source then, the required gas of another kind of target reaction of laser splash is carried out in feeding, adjust another kind of target position simultaneously, make laser beam successively by optical beam splitting sheet and focus lamp, see through the side of substrate vertical focusing to another kind of target, beginning sputter for the second time, described second time sputtering time with the first time sputtering time identical, keep the target rotation in the course of reaction, so that target can be by the even sputter of laser beam; Reaction finishes, and closes laser and can stop insulation simultaneously, can form heterogeneous p-n nano-line array on substrate surface; Described two kinds of different targets are respectively n type target and p type target, and n type target and p type target all are parallel to laser beam, and described substrate center is apart from target center position 2～7cm.
In order to realize the present invention further, described n type target is that purity is that 99.99% zinc oxide (ZnO) ceramic target or the purity of mixing the MgO of 20% (molar percentage) are 99.99% zinc oxide (ZnO) ceramic target; Described p type target is 99.99% gallium oxide (Ga for the purity of MgO of mixing 20% (molar percentage)
2O
3) ceramic target.
Described reacting furnace is a T type quartz ampoule, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm (this thickness is determined by the size of the molybdenum rod of equipment).
The rotating speed of described target rotation be 100 the step/minute about; The thermocouple position of described heating furnace and the residing position of target (reaction source) are on same upright position.
The described required gas of any target reaction that carries out laser splash comprises nitrogen or nitrogen and ammonia, and the gas required with the reaction of n type target is nitrogen; The described gas that reacts required with p type target is nitrogen and ammonia, and nitrogen: the ammonia volume ratio is 1: 3.
Described laser is that wavelength is that 532nm, pulsewidth are the pulse laser of the Nd:YAG of 10ns; The pulse frequency of described laser beam is 1～10Hz, and laser energy density is 1.6～8J/cm
2Described optical beam splitting sheet is 5/5 (half-reflection and half-transmission) beam splitting chip, 1/9 (saturating anti-nine) beam splitting chip or 2/8 (saturating two anti-eight) beam splitting chip.
Described substrate comprises monocrystalline silicon or Sapphire Substrate; The area of described monocrystalline substrate is 1 * 1mm
2～10 * 10mm
2, and be sprayed with the electrum of 5～15s in the above; Described Sapphire Substrate is Sapphire Substrate (being the axial Sapphire Substrate of c) of (0001) mirror polish or the Sapphire Substrate (being the axial Sapphire Substrate of a) of (1102) mirror polish.
Heterogeneous p-n nano-line array by method for preparing can be widely used in diode, triode or the various semi-conductor electronic device.
The above-mentioned method for preparing heterogeneous p-n also can be widely used in the preparation of other one-dimensional nano structure p-n junctions, and the difference that only needs to change reaction source and each reaction source according to need of work is mixed, and can obtain the p-n junction of different performance.Also can be widely used in the preparation of other heterostructures such as superlattice and homogeneity heterojunction (as above-mentioned zinc oxide homogeneity heterojunction).
It is as follows that the present invention utilizes pulsed laser deposition technique to prepare the principle of heterogeneous p-n nano-line array under the environment of HTHP: on the parallel rotation molybdenum rod that is positioned in the T type quartz ampoule of two kinds of different targets, make pulsed laser beam focus on the side of target, utilize the high-energy of pulse laser, make the surface mass fusion of target also and then at the target upper surface form plasma plume by laser ablation, this plasma plume body is splashed on the substrate (monocrystalline silicon or Sapphire Substrate), under the effect of the particle of the electrum of fusion on the substrate, nucleation also is oriented growth, and then grow up to nano wire gradually.After primary laser pulse finishes, can be on substrate the nano wire of shape face n type or p type, regulate target then, on the nano wire of established n type or p type, form the nano wire of p type or n type with same process with pulsed laser beam, thereby the formation p-n junction has so just been finished the preparation process of the nano-wire array of p-n junction.
The present invention compared with prior art has following advantage and beneficial effect:
The present invention utilizes the HTHP pulse laser sediment method to synthesize heterogeneous p-n nano-line on solid wire.Preparation technology of the present invention is simple to operate, and is not high to temperature and vacuum requirements, and used laser also is in long-wave band, reaction time is short, it is less influenced by other extraneous factors, can reach the stoichiometric of comparison strictness, helps the integrated production in enormous quantities of industrialization.The temperature of thousands of degree that the reaction temperature that the present invention adopts is more required than chemical method is much lower; Various experiment parameters are regulated easily; Used vacuum furnace is a T type quartz ampoule, and the metal vacuum stove cost used compared with other vacuum equipments is lower; Reaction time is short, and general chemical method is all wanted several hrs, have in addition want tens hours, and the inventive method only needed about one hour, even shorter; The preparation of the easy control material of preparation method of the present invention, growth material can be controlled by the control reaction source, makes the material composition uniformity.The heterogeneous p-n that the present invention synthesizes, a large amount of p-n junctions that use in the semiconductor device on solid wire, have been prepared, linear p-n junction is better than the performance of at present used membrane structure, interface loss diminishes, life-span increases, and its linear structure can be advantageously used in the preparation and the assembling field of semi-conductor electronic device.
Another outstanding characteristics of the present invention are to control the density of p-n junction nano-wire array and the position of diameter, length and the p-n junction of the p-n junction nano wire of forming this nano-wire array easily, can be by changing the distance between substrate and the target, the substrate situation, the laser pulse number of each target and the pulse energy of laser, pulse frequency wait the p-n junction nano-wire array of regulating final formation.Distance is more little between substrate and the target, and the underlayer temperature laser pulse number is many more, laser energy is big more, and frequency is big more, and the density of resulting nano-wire array will be big more.Can select suitable adjusting according to various application, prepare optimized nano-wire array.
Description of drawings
Fig. 1 prepares the installation drawing of p type gallium nitride/n type zinc oxide nano-wire array for the present invention adopts pulsed laser deposition technique.
Fig. 2 is the schematic diagram of heterogeneous p-n heterojunction nanowire array of the present invention, and wherein 21 is substrate, and grey color part 22 is a n type zinc oxide, and white portion 23 is a p type gallium nitride.
Fig. 3 is the schematic diagram of p type gallium nitride of the present invention/zinc oxide heterogeneous nano-wire array of n type, and wherein 31 is substrate, and grey color part 32 is a n type zinc oxide, and white portion 33 is a p type gallium nitride.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
As shown in Figure 1, equipment of the present invention has comprised laser 11, beam splitting chip 5, focus lamp 6, annular target (1) 3, annular target (2) 4, T type quartz ampoule 9, heating furnace 10, electric rotating machine 1, molybdenum rod 2.Wherein 7 be gas inlet, 13 for the outlet of gas, 8 for substrate, 12 for placing the quartz cell of substrate.
In this device, main reacting furnace is a T type quartz ampoule 9, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm; The molybdenum rod 2 that its T word bottom is equipped with electric rotating machine 1 and is driven by it, T word top is the key reaction position, and the gateway of gas, target position, substrate location and laser beam are all at this position, and they are on same straight line.The centre of this T type quartz ampoule is arranged in heating furnace 10, and the heating furnace galvanic couple is in the outside in quartz ampoule T word three intersection centres, and the thermocouple position of heating furnace and the residing position of reaction source are on same upright position.
The annular target is of a size of internal diameter 5～6mm, external diameter 15～25mm, thickness 5～8mm.Wherein annular target (1) 3 is 99.99% zinc oxide (ZnO) ceramic target for purity, and annular target (2) 4 is 99.99% gallium oxide (Ga for the purity of the MgO that mixes 20% (molar percentage)
2O
3) ceramic target, above-mentioned two targets are installed in parallel in resistant to elevated temperatures molybdenum rod 2 ends.The monocrystalline silicon (the perhaps axial Sapphire Substrate of a) 8 that is sprayed with the 5s electrum is put into a little quartz cell 12, again this quartz cell 12 is put into T type quartz ampoule 9, and making substrate center apart from target center position 2～7cm, substrate 8 is between target and laser beam sources.
With 9 forvacuum of T type quartz ampoule, when vacuum degree reaches 10
-2During Pa, stop to vacuumize, feed nitrogen (N
2), the maintenance nitrogen flow is 35～40sccm, and to keep in the T type quartz ampoule 9 air pressure be 2Torr (1Torr=1/760 standard atmospheric pressure=133Pa).Behind the air pressure steady air current, begin to heat, rate of warming is about 20～50 ℃/minute, heat to 600 ℃, open laser, adjust light path, make laser beam successively by optical beam splitting sheet and focus lamp, see through the substrate vertical focusing and in above-mentioned purity be on 99.99% the zinc-oxide ceramic target 3, sputter for the first time begins.Sputtering time is 30 minutes (about 9000 pulses), and energy density is about 8J/cm
2After sputter for the first time finishes, change feeding gas, make that the air-flow and the air pressure that feed gas are all constant, but gas changes nitrogen into: ammonia, volume ratio are 1: 3.Adjust the target position simultaneously, make laser beam successively by optical beam splitting sheet and focus lamp, seeing through the substrate vertical focusing is the side of 99.99% the p type gallium oxide ceramic target 4 of mixing in the purity of the above-mentioned 20%MgO of mixing, beginning sputter for the second time, and this process temperature remains unchanged.Sputtering time is similarly 30 minutes (about 9000 pulses) for the second time, and energy density still is 8J/cm
2Keep the target rotation in the course of reaction so that target can be by the even sputter of laser beam, the rotating speed that electric rotating machine drives the target rotation be 100 the step/minute about; Sputter for the second time can form heterogeneous p-n nano-line array after finishing on substrate surface; Allow T type quartz ampoule natural cooling, after T type quartz ampoule is reduced to room temperature (20～25 ℃), can take out sample.Can under electron microscope, see the heterojunction nanowire array that heterogeneous p-n is arranged on the monocrystalline substrate (the perhaps axial Sapphire Substrate of a) 8 that is being sprayed with the 5s electrum, as shown in Figure 2, nano wire among the figure on the substrate, grey color part are n type zinc oxide, and white portion is a p type gallium nitride.The diameter of the nano wire of preparing is that 50nm～500nm does not wait, about 1～20 micron of length.
The p-n junction nanometer rods for preparing can be used for preparing semiconductor device, because zinc oxide and gallium nitride are wide bandgap material, this p-n junction can be used for luminescent device.For example be widely used in light-emitting diodes such as traffic lights, instrument backlight, landscape light in city in the life now.A p-n junction is exactly a diode, as the p-n junction of nano wire, has reduced the interfacial effect of film p-n junction, reduces loss, can improve the luminous efficiency of light-emitting diode greatly, has increased the useful life of this diode simultaneously.
As shown in Figure 1, equipment of the present invention has comprised laser 11, beam splitting chip 5, focus lamp 6, annular target (1) 3, annular target (2) 4, T type quartz ampoule 9, heating furnace 10, electric rotating machine 1, molybdenum rod 2.Wherein 7 be gas inlet, 13 for the outlet of gas, 8 for substrate, 12 for placing the quartz cell of substrate.
In this device, main reacting furnace is a T type quartz ampoule 9, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm; The molybdenum rod 2 that its T word bottom is equipped with electric rotating machine 1 and is driven by it, T word top is the key reaction position, and gas inlet and outlet, target position, substrate location and laser beam are all at this position, and they are on same straight line.The centre of this T type quartz ampoule is arranged in heating furnace 10, and the heating furnace galvanic couple is in the outside in quartz ampoule T word three intersection centres.
The annular target is of a size of internal diameter 5～6mm, external diameter 15～25mm, thickness 5～8mm.Wherein annular target (1) 3 is 99.99% zinc oxide (ZnO) ceramic target for purity, and annular target (2) 4 is 99.99% gallium oxide (Ga for the purity of the MgO that mixes 20% (molar percentage)
2O
3) ceramic target, with parallel resistant to elevated temperatures molybdenum rod 2 ends of packing into of two targets.The monocrystalline silicon or the axial Sapphire Substrate of a that are sprayed with the 15s electrum are put into a little quartz cell, again this quartz cell is put into T type quartz ampoule.Substrate center is apart from target center position 2～7cm, and substrate 8 is between target and laser beam sources.
With 9 forvacuum of T type quartz ampoule, when vacuum degree reaches 10
-3During Pa, stop to vacuumize, feed nitrogen (N
2), the maintenance nitrogen flow is 35～40sccm, and air pressure is 2Torr in the maintenance T type quartz ampoule 9.Behind the air pressure steady air current, begin to heat, rate of warming is about 20～50 ℃/minute, heat to 1000 ℃, open laser, adjust light path, be the side of 99.99% zinc-oxide ceramic target 3 in above-mentioned purity with the laser beam vertical focusing, sputter for the first time begins.Sputtering time is 30 minutes (about 9000 pulses), and energy density is about 8J/cm
2After sputter for the first time finishes, regulate feeding gas, make that the air-flow and the air pressure that feed gas are all constant, but gas changes nitrogen into: ammonia, volume ratio are 1: 3.Adjust the target position simultaneously, make that the laser beam vertical focusing is on 99.99% the p type gallium oxide ceramic target 4 of mixing in the purity of the above-mentioned 20%MgO of mixing, beginning sputter for the second time, this process temperature remains unchanged.Sputter for the second time is similarly 30 minutes (about 9000 pulses), and energy density still is 8J/cm
2Keep the target rotation in the course of reaction so that target can be by the even sputter of laser beam, the rotating speed that electric rotating machine drives the target rotation be 100 the step/minute about; Sputter for the second time can form heterogeneous p-n nano-line array after finishing on substrate surface; T type quartz ampoule natural cooling after T type quartz ampoule is reduced to room temperature, can take out sample.Can under electron microscope, see the heterojunction nanowire array that heterogeneous p-n is arranged on the monocrystalline substrate (the perhaps axial Sapphire Substrate of a) that is being sprayed with the 15s electrum, as shown in Figure 2, nano wire on the substrate, grey color part are n type zinc oxide, and white portion is a p type gallium nitride.The diameter of the nano wire of preparing is that 50nm～300nm does not wait, about 20～50 microns of length.
As shown in Figure 1, equipment of the present invention has comprised laser 11, beam splitting chip 5, focus lamp 6, annular target (1) 3, annular target (2) 4, T type quartz ampoule 9, heating furnace 10, electric rotating machine 1, molybdenum rod 2.Wherein 7 be gas inlet, 13 for the outlet of gas, 8 for substrate, 12 for placing the quartz cell of substrate.
In this device, main reacting furnace is a T type quartz ampoule 9, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm; The molybdenum rod 2 that its T word bottom is equipped with electric rotating machine 1 and is driven by its, T word top is the key reaction position, gas inlet and outlet, the target position, substrate location, and laser beam is all at this position, they are on same straight line.The centre of this T type quartz ampoule is arranged in heating furnace 10, and the heating furnace galvanic couple is in the outside in quartz ampoule T word three intersection centres.
The annular target is of a size of internal diameter 5～6mm, external diameter 15～25mm, thickness 6～8mm.Wherein annular target (1) 3 is 99.99% zinc oxide (ZnO) ceramic target for purity, and annular target (2) 4 is 99.99% gallium oxide (Ga for the purity of the MgO that mixes 20% (molar percentage)
2O
3) ceramic target, with parallel resistant to elevated temperatures molybdenum rod 2 ends of packing into of two targets.With being sprayed with the monocrystalline substrate (the perhaps axial Sapphire Substrate of c) 8 of 15s electrum, put into a little quartz cell, again this quartz cell is put into T type quartz ampoule.Substrate center is apart from target center position 2～7cm, and substrate 8 is between target and laser beam sources.
The forvacuum of T quartz ampoule is when vacuum degree reaches 10
-2During Pa, stop to vacuumize, feed nitrogen: the ammonia volume ratio is 1: 3 a gas, and maintenances gas flow is 35～40sccm, and air pressure is 5Torr (1Torr=1/760 standard atmospheric pressure=133Pa) in the maintenance T type quartz ampoule.Behind the air pressure steady air current, begin to heat, rate of warming is about 20～50 ℃/minute, heat to 700 ℃, open laser, adjust light path, be the side of 99.99% gallium oxide ceramic target 4 in above-mentioned purity of mixing 20% MgO with the laser beam vertical focusing, sputter for the first time begins.Sputtering time is 20 minutes (about 12000 pulses), and energy density is about 3.6J/cm
2After sputter for the first time finishes, regulate feeding gas, make that the air-flow and the air pressure that feed gas are all constant, but gas changes nitrogen (N into
2).Adjust the target position simultaneously, make that the laser beam vertical focusing is the side of 99.99% zinc-oxide ceramic target 3 in above-mentioned purity, beginning sputter for the second time, this process temperature remains unchanged.Sputter for the second time is similarly 20 minutes (about 12000 pulses), and energy density still is 3.6J/cm
2Keep the target rotation in the course of reaction so that target can be by the even sputter of laser beam, the rotating speed that electric rotating machine drives the target rotation be 100 the step/minute about; Sputter for the second time can form heterogeneous p-n nano-line array after finishing on substrate surface; Allow T type quartz ampoule natural cooling, after T type quartz ampoule is reduced to room temperature, can take out sample.Can under electron microscope, see the heterojunction nanowire array that p type gallium nitride/n type zinc oxide is arranged in the monocrystalline substrate that is sprayed with the 15s electrum (the perhaps axial Sapphire Substrate of c), as shown in Figure 3, nano wire among the figure on the substrate, the ash color part is a n type zinc oxide, and white portion is a p type gallium nitride.The diameter of the nano wire of preparing is that 50nm～500nm does not wait, about 1～20 micron of length.
Can change the sputter order of its material according to practical application, to adapt to different application.
Embodiment 4
As shown in Figure 1, equipment of the present invention has comprised laser 11, beam splitting chip 5, focus lamp 6, annular target (1) 3, annular target (2) 4, T type quartz ampoule 9, heating furnace 10, electric rotating machine 1, molybdenum rod 2.Wherein 7 be gas inlet, 13 for the outlet of gas, 8 for substrate, 12 for placing the potsherds of substrate.
In this device, main reacting furnace is a T type quartz ampoule 9, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm; The molybdenum rod 2 that its T word bottom is equipped with electric rotating machine 1 and is driven by it, T word top is the key reaction position, and gas inlet and outlet, target position, substrate location and laser beam are all at this position, and they are on same straight line.The centre of this T type quartz ampoule is arranged in heating furnace 10, and the heating furnace galvanic couple is in the outside in quartz ampoule T word three intersection centres.
The annular target is of a size of internal diameter 5～6mm, external diameter 15～25mm, thickness 6～8mm.Wherein annular target (1) 3 is 99.99% zinc oxide (ZnO) ceramic target for purity, and annular target (2) 4 is 99.99% gallium oxide (Ga for the purity of the MgO that mixes 20% (molar percentage)
2O
3) ceramic target, with parallel resistant to elevated temperatures molybdenum rod 2 ends of packing into of two targets.With being sprayed with the monocrystalline substrate (the perhaps axial Sapphire Substrate of c) of 15s electrum, put into a little potsherd, again this potsherd is put into T type quartz ampoule.Substrate center is apart from target center position 2～7cm, and substrate 8 is between target and laser beam sources.
The forvacuum of T quartz ampoule is when vacuum degree reaches 10
-2During Pa, stop to vacuumize, feed nitrogen: the ammonia volume ratio is 1: 3 a gas, and the maintenance gas flow is 35～40sccm, and air pressure is 1Torr in the maintenance T type quartz ampoule.Behind the air pressure steady air current, begin to heat, rate of warming is about 20～50 ℃/minute, heat to 700 ℃, open laser, adjust light path, be the side of 99.99% gallium oxide ceramic target 4 in above-mentioned purity of mixing 20% MgO with the laser beam vertical focusing, sputter for the first time begins.Sputtering time is 60 minutes (about 12000 pulses), and energy density is about 8J/cm
2After sputter for the first time finishes, regulate feeding gas, make that the air-flow and the air pressure that feed gas are all constant, but gas changes nitrogen (N into
2).Adjust the target position simultaneously, make that the laser beam vertical focusing is the side of 99.99% zinc-oxide ceramic target 3 in above-mentioned purity, beginning sputter for the second time, this process temperature remains unchanged.Sputter for the second time is similarly 60 minutes (about 12000 pulses), and energy density still is 8J/cm
2Keep the target rotation in the course of reaction so that target can be by the even sputter of laser beam, the rotating speed that electric rotating machine drives the target rotation be 100 the step/minute about; Sputter for the second time can form heterogeneous p-n nano-line array after finishing on substrate surface; T type quartz ampoule natural cooling after T type quartz ampoule is reduced to room temperature, can take out sample.Can under electron microscope, see the heterojunction nanowire array that p type gallium nitride/n type zinc oxide is arranged on the monocrystalline substrate (the perhaps axial Sapphire Substrate of c) at the metal spraying silver alloy, as shown in Figure 3, nano wire on the substrate, grey color part are n type zinc oxide, and white portion is a p type gallium nitride.The diameter of the nano wire of preparing is that 50nm～500nm does not wait, about 5～20 microns of length.
As shown in Figure 1, equipment of the present invention has comprised laser 11, beam splitting chip 5, focus lamp 6, annular target (1) 3, annular target (2) 4, T type quartz ampoule 9, heating furnace 10, electric rotating machine 1, molybdenum rod 2.Wherein 7 be gas inlet, 13 for the outlet of gas, 8 for substrate, 12 for placing the quartz cell of substrate.
In this device, reacting furnace is a T type quartz ampoule 9, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm; The molybdenum rod 2 that its T word bottom is equipped with electric rotating machine 1 and is driven by it, T word top is the key reaction position, and gas inlet and outlet, target position, substrate location and laser beam are all at this position, and they are on same straight line.The centre of this T type quartz ampoule is arranged in heating furnace 10, and the heating furnace galvanic couple is in the outside in quartz ampoule T word three intersection centres.
The annular target is of a size of internal diameter 5～6mm, external diameter 15～25mm, thickness 5～8mm.Wherein annular target (1) 3 is that the purity of the MgO of doping 20% (molar percentage) is 99.99% zinc oxide (ZnO) ceramic target, and annular target (2) 4 is 99.99% gallium oxide (Ga for the purity of mixing 20% (molar percentage) MgO
2O
3) ceramic target, with parallel resistant to elevated temperatures molybdenum rod 2 ends of packing into of two targets.The monocrystalline substrate (the perhaps axial Sapphire Substrate of a) that is sprayed with the 15s electrum is put into a little quartz cell, again this quartz cell is put into T type quartz ampoule.Substrate center is apart from target center position 2～7cm, and substrate 8 is between target and laser beam sources.
With the forvacuum of T quartz ampoule, when vacuum degree reaches 10
-2During Pa, stop to vacuumize, feed nitrogen (N
2), the maintenance nitrogen flow is 35～40sccm, and air pressure is 5Torr in the maintenance T type quartz ampoule.Behind the air pressure steady air current, begin to heat, rate of warming is about 20～50 ℃/minute, heat to 800 ℃, open laser, adjust light path, be the side of 99.99% zinc-oxide ceramic target 3 in the purity of the MgO of above-mentioned doping 20% with the laser beam vertical focusing, sputter begins.Sputtering time is 60 minutes (about 12000 pulses), and energy density is about 1.6J/cm
2After sputter for the first time finishes, regulate feeding gas, make that the air-flow and the air pressure that feed gas are all constant, but gas changes nitrogen into: ammonia, volume ratio are 1: 3.Adjust the target position simultaneously, make that the laser beam vertical focusing is the side of 99.99% gallium oxide ceramic target 4 in the purity of the above-mentioned 20%MgO of mixing, beginning sputter for the second time, this process temperature remains unchanged.Sputter for the second time is similarly 60 minutes (about 12000 pulses), and energy density still is 1.6J/cm
2Keep the target rotation in the course of reaction so that target can be by the even sputter of laser beam, the rotating speed that electric rotating machine drives the target rotation be 100 the step/minute about; Sputter for the second time can form heterogeneous p-n nano-line array after finishing on substrate surface; Allow T type quartz ampoule natural cooling, after T type quartz ampoule is reduced to room temperature, can take out sample.Can under electron microscope, see the heterojunction nanowire array that heterogeneous p-n is arranged on the monocrystalline substrate (the perhaps axial Sapphire Substrate of a) that is being sprayed with the 15s electrum, as shown in Figure 2, nano wire on the substrate, the ash color part is n type zinc oxide (mixing the zinc oxide of magnesium), and white portion is p type gallium nitride (mixing the gallium nitride of magnesium).The diameter of the nano wire of preparing is that 50nm～500nm does not wait, about 20～50 microns of length.
Present embodiment has changed n section bar material, also can change different n types or p section bar material as embodiment 5, prepares various heterogeneous p-n nano-line arrays under appropriate condition, thereby is used for the semiconductor device of different performance.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1, a kind of preparation method of heterogeneous p-n nano-line array, comprise the steps: two kinds of different targets are installed in parallel on the molybdenum rod of the electric rotating machine in the reacting furnace, substrate is positioned in a quartz cell or the potsherd, again this quartz cell or potsherd are positioned in the reacting furnace, make quartz cell or potsherd, target place heating furnace; With this reacting furnace forvacuum, reach 10
-3～10
-2Behind the Pa, speed with 35～50sccm feeds the required gas of any target reaction that carries out laser splash, make that air pressure reaches 1～5Torr in the reacting furnace, reacting furnace is heated after 600～1000 ℃ then, regulate laser, make the laser emission laser beam successively by optical beam splitting sheet and focus lamp, see through the side of substrate vertical focusing, target was carried out laser splash 20～60 minutes to target; Change gas source then, the required gas of another kind of target reaction of laser splash is carried out in feeding, adjust another kind of target position simultaneously, make laser beam successively by optical beam splitting sheet and focus lamp, see through the side of substrate vertical focusing to another kind of target, beginning sputter for the second time, described second time sputtering time with sputtering time is identical for the first time, keep target to rotate in the course of reaction; Reaction finishes, and closes laser and can stop insulation simultaneously, promptly forms heterogeneous p-n nano-line array on substrate surface; Described two kinds of different targets are respectively n type target and p type target, and n type target and p type target all are parallel to laser beam, and described substrate center is apart from target center position 2～7cm.
2, the preparation method of heterogeneous p-n nano-line array according to claim 1 is characterized in that: described n type target is that purity is 99.99% zinc-oxide ceramic target or to mix molar percentage be that the purity of 20% MgO is 99.99% zinc-oxide ceramic target; Described p type target is that to mix molar percentage be that the purity of 20% MgO is 99.99% gallium oxide ceramic target.
3, the preparation method of heterogeneous p-n nano-line array according to claim 3 is characterized in that: described reacting furnace is a T type quartz ampoule, and its internal diameter is 40～45mm, and external diameter is 45～50mm, and thickness is 5mm～10mm.
4, the preparation method of heterogeneous p-n nano-line array according to claim 1, it is characterized in that: the described required gas of any target reaction that carries out laser splash comprises nitrogen or nitrogen and ammonia, and the gas required with the reaction of n type target is nitrogen; The described gas that reacts required with p type target is nitrogen and ammonia, and nitrogen: the ammonia volume ratio is 1:3.
5, the preparation method of heterogeneous p-n nano-line array according to claim 1 is characterized in that: the rotating speed of described target rotation be 100 the step/minute.
6, the preparation method of heterogeneous p-n nano-line array according to claim 1 is characterized in that: described laser is that wavelength is that 532nm, pulsewidth are the pulse laser of the Nd:YAG of 10ns; The pulse frequency of described laser beam is 1～10Hz, and laser energy density is 1.6～8J/cm
2Described optical beam splitting sheet is 5/5 beam splitting chip, 1/9 beam splitting chip or 2/8 beam splitting chip.
7, the preparation method of heterogeneous p-n nano-line array according to claim 1 is characterized in that: described substrate comprises monocrystalline substrate or Sapphire Substrate; The area of described monocrystalline silicon is 1 * 1mm
2～10 * 10mm
2Described Sapphire Substrate is Sapphire Substrate of (0001) mirror polish or the Sapphire Substrate of (1102) mirror polish.
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| CN102050426B (en) * | 2009-11-10 | 2013-06-12 | 北京邮电大学 | Method for preparing heterogeneous nanowire |
| CN105947974A (en) * | 2016-05-03 | 2016-09-21 | 济南大学 | Cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth |
| CN106544729B (en) * | 2016-11-24 | 2018-12-28 | 国家纳米科学中心 | A kind of GaN-ZnO solid solution nano wire, preparation method and the usage |
| CN111468104B (en) * | 2019-10-15 | 2021-07-16 | 中山大学 | Preparation method and application of graphene-bismuth tungstate |
| CN111162141A (en) * | 2019-12-20 | 2020-05-15 | 燕山大学 | Preparation method of multi-junction nanowire solar cell |
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