CN100410417C - Method for preparing thin film material of metal zirconium - Google Patents
Method for preparing thin film material of metal zirconium Download PDFInfo
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- CN100410417C CN100410417C CNB2004101018850A CN200410101885A CN100410417C CN 100410417 C CN100410417 C CN 100410417C CN B2004101018850 A CNB2004101018850 A CN B2004101018850A CN 200410101885 A CN200410101885 A CN 200410101885A CN 100410417 C CN100410417 C CN 100410417C
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Abstract
The present invention relates to a method for preparing film materials of metal zirconium, which belongs to the technical field of semiconductors. The method uses a double-ion beam epitaxy growth device which has a mass separation function and a charge energy ion deposition characteristic, and zirconium chloride with low purity and low cost is used as a raw material; single-beam isotopically pure low-energy argon ions are used for bombarding a washed clean substrate; a produced isotopically pure low-energy zirconium ion beam and a nitrogen ion beam are used for preparing a layer of zirconium nitride as a barrier layer and a buffer layer for avoiding the interface reaction of the substrate and zirconium ions; the single-beam isotopically pure low-energy metal zirconium ions can epitaxially generate a metal zirconium film; via the accurate control of the energy, the deposition amount, the beam current density, the beam spot shape and the growth temperature of the zirconium ion beam, the metal zirconium film with the characteristics of hard purification and high melting point can grow with high purity, high efficiency and high quality and extends at low temperature in an ultrahigh vacuum growth chamber. The growth process is convenient to adjust, control and optimize, and is an economical and practical method for preparing film materials of metal zirconium.
Description
Technical field
The invention belongs to technical field of semiconductors, refer in particular to a kind of ion beam epitaxy (IBE) growth apparatus that utilizes, prepare the method for difficult purification, high-melting point metal zirconium (Zr) thin-film material.
Background technology
IVB family refractory metal zirconium (Zr) is as the important strategic material, its metal and compound are widely used in many fields of national economy and national defense construction, particularly, along with developing rapidly of information electronic technology in recent years, its application of technical field of semiconductors especially extremely people pay attention to.Such as, at microelectronic, the continuous increase of super large-scale integration (ULSI) scale, make device feature size constantly reduce, this just need to seek new, performance better, the insulated gate electrode material, diffusion barrier material and the Ohm contact electrode material that are adapted at using under the small scale, and the oxide compound of zirconium, nitride and metallic film can be expected to become the ideal candidates material that following microelectronics this respect needs.And with regard to the metallic film of zirconium (Zr), because of it has good thermostability (fusing point is 1930 ℃), strong anticorrosion properties, good electrical conductivity (room temperature resistivity is 40 μ Ω .cm) and and silicon (Si) between littler lattice mismatch (0.967%) and thermal expansion coefficient difference are arranged, get a good chance of becoming and the present technical field of semiconductors the same important meals thin-film material of metal titanium film commonly used, and at high temperature, high frequency, application on microelectronic device of using under the extreme conditions such as high pressure and the powerful opto-electronic device is expected the high temperature Ohm contact electrode material that the alternative metals titanium becomes a new generation, it should be noted that, the lattice parameter of metal zirconium film, thermal expansivity and important third generation compound semiconductor materials--gan (GaN) also all very approaching, and because it has stable hexagonal closs packing structure below 870 ℃, and the temperature of molecular beam epitaxy (MBE) method growing gallium nitride is generally 700 to 800 ℃, so become the desirable cushioning layer material of MBE method growing GaN epitaxial film probably, though metal current zirconium (Zr) film has been obtained some progress in the application of technical field of semiconductors, but owing to compare prices of raw and semifnished materials height with titanium (Ti), and its difficult purification, dystectic characteristic is more obvious, make that preparation is high-purity, the cost of the metal zirconium film of high crystalline quality is very high, and growing technology is also not as titanium (Ti) maturation.
The common method of preparation growing metal zirconium film mainly contains magnetron sputtering, pulsed laser deposition (PLD), ion beam assisted depositing (IBAD) and electron beam evaporation etc. at present, but existing these common methods also have the following disadvantages:
1) existing preparation growth method commonly used requires all very highly usually to purity of raw materials, and highly purified to contain the zirconium starting material much more expensive than the titaniferous prices of raw and semifnished materials of same purity.With regard to magnetically controlled sputter method the most frequently used in the metal zirconium film preparation, melting prepares refractory metal zirconium target, and complex process does not say that the preparation process of metal zirconium target is also oxidized easily, and purity also is difficult to guarantee.Because of the difficult expensive problem of purifying and bringing of starting material, restricted metal current zirconium film greatly and used widely and promote at semiconductor applications;
2) existing preparation growth method commonly used, its process of growth all be usually have back work gas than the rough vacuum environment under grow, so be unfavorable for obtaining film high-purity, high crystalline quality.The impurity particularly introducing of oxygen can reduce the crystalline quality and the specific conductivity of film, and then influences device performance;
3) existing preparation growth method commonly used, its growth temperature is all higher usually, in the starting stage of growth, forming silicide or other intermediate compounds at the interface possibly, and increase contact resistance and influence the quality that subsequent thin film is grown, needing low underlayer temperature (below 560 ℃), also is the requirement of present microelectronics;
4) existing preparation growth method commonly used, the aspects such as planeness of internal stress, raising film surface are also not fully up to expectations in reducing metal zirconium film rete.Surface undulation is unfavorable for the carrying out of secondary epitaxy and subsequent technique greatly, and is big as big blocking effect difference of pinhold density and leakage current, and the mechanical property of film is bad also may to be influenced subsequent technique and carry out use properties with device.
Based on above-mentioned analysis, how to reduce the cost of metal zirconium film preparation, obtain high-quality thin film high-purity, that have an even surface, develop a kind of more sophisticated preparation growing technology, being still still needs the problem that solves in the metal current zirconium film preparing technology research.
A kind of new thin-film material preparation method--ion beam epitaxy (IBE) appears in the early 1990s in 20th century, also claims the low energy ion beam deposition of mass separation sometimes.Because of it has unique mass separation function and energetic ion sedimentary characteristic, can make the purification and the thin film epitaxial growth of material finish in same process, difficult purification, high-melting-point, the metal of easily oxidation and the Perfected process of binary compound thin-film material are considered to grow.The growing system that this method adopted, its ionic fluid part has dual beam structure usually, every bundle has independently devices such as ion source, magnetic analyzer, electric or magnetic quadrupole lens and electrostatic deflection electrodes, the shared retarding lens device of two-beam is positioned at the growth room, the mode that the vacuum design of whole growth system adopts difference to bleed designs, vacuum from the ion source to the growth room improves step by step, the dynamic vacuum degree of ultrahigh vacuum(HHV) growth room≤5.0 * 10
-7Pa.The ion source of this system almost can produce the ion of total mass number from 1 (H) to all elements of 208 (Pb) in the periodic table of elements, and selects to purify according to total mass number by the magnetic analyzer device of this system.With purity is not the material ion that very high starting material can produce isotopic pure, and realizes the ultrapure growth and the low temperature high-quality extension of film in the ultrahigh vacuum(HHV) growth room, is a big characteristic of this method.The low energy ion beam epitaxial method of mass separation is being achieved success aspect the growing and preparing research of rare earth thin-film material at present, but the increment study that utilizes this method how to carry out high-melting-point, difficult transition group IVB family refractory metal film of purifying also rarely has report.The purpose of this invention is to provide a kind of ion beam epitaxy (IBE) growth apparatus that utilizes, the preparation growth can be applicable to the difficulty purification of technical field of semiconductors, the method for refractory metal zirconium (Zr) thin-film material.
Summary of the invention
The invention provides a kind of ion beam epitaxy (IBE) growth apparatus that utilizes, prepare the method for difficult purification, high-melting point metal zirconium (Zr) thin-film material.Purpose is to reduce the preparation cost of metal zirconium (Zr) thin-film material, realizes that it is high-purity, the growth of the high-quality of high crystalline quality and low-temperature epitaxy, develops a kind of economical and practical method that growth is applied to technical field of semiconductors metal zirconium (Zr) thin-film material for preparing.
For achieving the above object, the technical scheme that technical solution problem of the present invention is adopted is:
A kind of method for preparing thin film material of metal zirconium is provided, its utilization has the double-ion beam epitaxial growth equipment of mass separation function and energetic ion sedimentary characteristic, with the not high low-cost zirconium chloride of purity requirement is starting material, on the clean silicon substrate of crossing with the isotopic pure low energy ion beam bombardment sputter clean of Dan Shu, prepare the thin zirconium nitride of one deck as the blocking layer and the buffer layer that stop silicon and zirconium ion generation surface reaction with isotopic pure low energy metal zirconium ionic fluid that produces and nitrogen ion beam earlier, use the isotopic pure low energy metal zirconium ion epitaxy metal zirconium film of Dan Shu again, energy by accurate control zirconium ion bundle, deposit dose, beam current density, bundle shape of spot and growth temperature, in the ultrahigh vacuum(HHV) growth room, realize difficult the purification, refractory metal zirconium film low-cost high-purity, high crystalline quality growth and low-temperature epitaxy.
The described method for preparing thin film material of metal zirconium is meant a kind of ion beam epitaxy growth apparatus that utilizes especially, on substrate, prepares the method for difficult purification, high-melting point metal zirconium thin-film material, comprises the steps:
Step 1: select the starting material of the not high low-cost zirconium chloride pressed powder of purity requirement for use as the Bai Nasi type solid ion source generation zirconium ion bundle of ion beam epitaxy growth apparatus I bundle, and in the evaporator type crucible with its Bai Nasi type solid ion source apparatus of packing into;
Step 2: select for use argon gas to produce the starting material of the ar-ion beam that is used for the cleaning of substrate surface dry method as the Bai Nasi type gas ion source of ion beam epitaxy growth apparatus II bundle;
Step 3: select for use nitrogen to be used for and the long starting material that approach the nitrogen ion beam of zirconium nitride buffer layer of zirconium ion fasciculation symphysis as the Bai Nasi type gas ion source generation of ion beam epitaxy growth apparatus II bundle;
Step 4: the substrate that will clean is inserted the growth room;
Step 5: the vacuum that detaches sub-beam epitaxy growth apparatus;
Step 6: two ion source bakings to the ion beam epitaxy growth apparatus are degassed;
Step 7: baking is degassed or is carried out the high temperature deoxidation treatment to the substrate in the growth room;
Step 8: the air-intake duct that the container and the Bai Nasi type gaseous ion source apparatus of ion beam epitaxy growth apparatus II bundle of splendid attire argon gas is outer is connected, by the noticeable degree charge flow rate on it, logical argon gas in ion source, and utilize this ionic fluid to produce the high-energy argon ion bundle of isotopic pure;
Step 9: open the ultrahigh vacuum(HHV) growth room of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, the high-energy argon ion bundle vertical incidence of isotopic pure is advanced in the retarding lens device in the ultrahigh vacuum(HHV) growth room, isotopic pure low energy ion beam bundle bombardment sputter substrate surface with deceleration obtains carries out the residual impurity that dry method is cleaned the substrate surface pickup;
Step 10: the ar-ion beam of closing ion beam epitaxy growth apparatus II bundle, the dry method that stops substrate being cleaned, close the growth room of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, close the needle-valve and the argon gas of Bai Nasi type gaseous ion source apparatus external admission conduit;
Step 11: the container of splendid attire nitrogen is connected with the Bai Nasi type gaseous ion source apparatus external admission conduit of ion beam epitaxy growth apparatus II bundle, by the noticeable degree charge flow rate on it, logical nitrogen in ion source utilizes this ionic fluid to produce the high energy nitrogen ion beam of isotopic pure;
Step 12: the temperature after the Bai Nasi type solid ion source apparatus baking that continues slow rising I bundle is degassed, make it slowly evaporate zirconium chloride atmosphere, by the working temperature in the control ion source, it is stable to keep its operating air pressure, and utilizes this ionic fluid to produce the high energy zirconium ion bundle of isotopic pure;
Step 13: open the growth room of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, utilize the timesharing cutting conducting function of ion source line regulation device, the high energy zirconium ion bundle of isotopic pure and nitrogen ion beam vertical incidence are alternately advanced in the retarding lens device in the ultrahigh vacuum(HHV) growth room, the isotopic pure low energy zirconium ion bundle and the nitrogen ion beam that slow down and obtain, the dosage and the proportioning of the cycle alternating deposit of setting according to the ion beam flow measuring apparatus, the thin zirconium nitride layer of preparation growth one deck is as stopping the blocking layer of substrate material and zirconium ion generation surface reaction and the buffer layer of growing metal zirconium film on substrate;
Step 14: close the nitrogen ion beam of ion beam epitaxy growth apparatus II bundle, stop the epitaxy of thin zirconium nitride buffer layer, close the air inlet needle-valve and the nitrogen of the Bai Nasi type gas ion source of II bundle;
Step 15: restraint the isotopic pure zirconium ion bundle that produces with ion beam epitaxy growth apparatus I separately, in the ultrahigh vacuum(HHV) growth room, with lower energy, epitaxy thin film material of metal zirconium on thin zirconium nitride buffer layer.
Vacuum tightness in the ion source before the described method for preparing thin film material of metal zirconium, the baking in its described step 6 are degassed≤10
-4Pa, the temperature of baking heating is controlled by adjusting its filament heating current, crucible heating current and arc chamber heating current in the Bai Nasi type solid ion source of I bundle, the temperature of this ion source baking heating is 120～140 ℃, the Bai Nasi type gas ion source of II bundle is controlled the temperature of baking heating by adjusting its filament heating current, and the baking Heating temperature is 〉=120 ℃.
The described method for preparing thin film material of metal zirconium, before the baking of substrate in its described step 7 is degassed the indoor vacuum tightness of growth should reach≤5 * 10
-6Pa by the Heating temperature that lining heat provides substrate baking to degas, degass or needs the temperature and time of high temperature deoxidation treatment, and according to the difference of substrate type and difference, maximum heating temperature is 800 ℃.
The described method for preparing thin film material of metal zirconium, the energy region of the isotopic pure low energy ion beam that is used for substrate surface bombardment sputter clean that it is described in carry out step 9 is 100 to 1KeV, beam current density is 50 to 100 μ A/cm
2, bundle spot size covers entire substrate, determines energy, beam current density and the scavenging period of the low energy ion beam that is used for cleaning according to the substrate type difference.
The described method for preparing thin film material of metal zirconium, the low energy zirconium ion bundle and the nitrogen ion beam of the isotopic pure that it is described to obtain after slowing down in carry out step 13, by the electric quadrupole lens devices and the electric field of auxiliary electric liner, magnetic quadrupole lens device and the magnetic field of auxiliary magnetic steering device and the electric field of electrostatic deflection electrodes device that II restraints of readjusting I bundle, make alternating deposit cover entire substrate, and big or small same position overlap to the two bundle spots of restrainting the low energy ion beam of isotopic pures on the substrate.
The described method for preparing thin film material of metal zirconium, energy region after the isotopic pure zirconium ion bundle of it is described being used in carry out step 13 the prepare thin zirconium nitride buffer layer of growth and nitrogen ion beam slow down is 15 to 1KeV, according to substrate type difference and the growth needs that growth is adopted, determine energy, beam current density and the alternating deposit dosage and the proportioning of the low energy ion of participation growth.
The described method for preparing thin film material of metal zirconium, it is described carry out step 13 in the time vacuum tightness≤5.0 * 10 in the ultrahigh vacuum(HHV) growth room
-6Pa, the preparation growth temperature of thin zirconium nitride buffer layer is provided by lining heat, and the intensification scope is a room temperature to 800 ℃, and the substrate type that is adopted according to growth is different and growth needs is definite.
The described method for preparing thin film material of metal zirconium, it is described carry out step 13 in the time, in process of growth, the scanning that swings of the Small angle by substrate further improves the thin epitaxially grown homogeneity of zirconium nitride buffer layer.
The described method for preparing thin film material of metal zirconium, the energy region of it is described being used in carry out step 15 the prepare isotopic pure low energy zirconium ion of growing metal zirconium film be 15eV to 1KeV, can be according to the substrate type that growth be adopted different and growth needs is definite.
The described method for preparing thin film material of metal zirconium, it is described carry out step 15 in the time vacuum tightness≤5 * 10 in the ultrahigh vacuum(HHV) growth room
-6Pa, preparation growing metal zirconium growth for Thin Film temperature is provided by lining heat, and the intensification scope is a room temperature to 800 ℃, and the substrate type that is adopted according to growth is different and growth needs is definite.
The described method for preparing thin film material of metal zirconium, the preparation growth of the metal zirconium film that it is described in carry out step 15, the scanning that can swing by the Small angle of substrate further improves the homogeneity of metal zirconium thin film epitaxial growth.
The described method for preparing thin film material of metal zirconium, the preparation growth of the metal zirconium film that it is described in carry out step 15, bundle spot size that can be by adjusting epitaxially grown low energy metal zirconium ionic fluid and sedimentary dosage come the area and the thickness of the metal zirconium film that control growing obtains.
The described method for preparing thin film material of metal zirconium, it is in vacuum tightness≤5 * 10
-6In the ultrahigh vacuum(HHV) growth room of Pa, adopt silicon as substrate, after substrate cleans through the isotopic pure low energy ion beam bundle bombardment sputter dry method of 300eV, underlayer temperature with 295 ℃～305 ℃, earlier with the 200eV isotopic pure low energy metal zirconium ionic fluid and the nitrogen ion beam that produce, alternating deposit prepares the thin zirconium nitride of one deck as the blocking layer and the buffer layer that stop silicon substrate and zirconium ion generation surface reaction, use the 200eV isotopic pure low energy metal zirconium ion epitaxy of Dan Shu again, prepare and have high crystalline quality metal zirconium film highly single-orientated and that smooth surface is smooth.
The described method for preparing thin film material of metal zirconium, wherein, the beam current density that is used for the low energy ion beam bundle of silicon substrate dry method cleaning is 100 μ A/cm
2, scavenging period is 2～3 minutes.
The described method for preparing thin film material of metal zirconium, wherein, the dosage that is used for alternating deposit in single cycle of the isotopic pure low energy zirconium ion bundle of thin zirconium nitride buffer layer preparation and nitrogen ion beam is 6.25 * 10
14Dose and 25.00 * 10
14Dose, total cycle count is 50, zirconium ion is 1 to 4 with nitrogen ionic deposit dose ratio.
The present invention compared with prior art has following beneficial effect:
The method of utilizing the ion beam epitaxy growth apparatus to prepare thin film material of metal zirconium of the present invention:
Utilize the bombardment sputter effect of the low energy ion beam of isotopic pure, in the ultrahigh vacuum(HHV) growth room, carrying out the dry method of substrate cleans, can thoroughly remove the residual impurity of substrate pickup, carry out the epitaxy of thin-film material with the substrate of cleaning, be more conducive to obtain metal zirconium film high-purity, high crystalline quality;
Very little thin zirconium nitride (ZrN) layer of the one deck that utilizes on the substrate growth earlier and metal zirconium film mismatch degree is as the buffer layer that stops that surface reaction blocking layer between zirconium ion and substrate and epitaxy are used, and is beneficial to realize that the high crystalline quality of metal zirconium film grows;
Utilize the unique qualities separation function and the ion retardation function of ion beam epitaxy growth apparatus, select the not high zirconium chloride (ZrCl of purity requirement for use
4) pressed powder and nitrogen is respectively as producing isotopic pure low energy metal zirconium ion (Zr
+) bundle and nitrogen ion (N
+) bundle starting material, reduced the material cost of thin zirconium nitride (ZrN) buffer layer and metal zirconium film preparation growth, and in the ultrahigh vacuum(HHV) growth room of no any back work gas, carry out the preparation growth of thin-film material, realized high-purity growth of the metal zirconium film of difficult purification;
Be used for carrying out the isotopic pure low energy metal zirconium ion (Zr of thin-film material preparation growth
+) and nitrogen ion (N
+), the film interaction with in substrate and the growth also can play the local heating effect, has realized the low-temperature epitaxy of thin zirconium nitride (ZrN) buffer layer and metal zirconium film;
Be used for carrying out the atomic state isotopic pure low energy metal zirconium ion (Zr of thin-film material preparation growth
+) and nitrogen ion (N
+), have better chemically reactive and have electric charge, can optimize growth technique by accurate control participation growth ionic deposit dose or proportioning, ion energy, ion beam spot shape and growth temperature, and then obtain to have thin zirconium nitride (ZrN) buffer layer of positive stoicheiometry and the smooth high crystalline quality metal zirconium film of smooth surface;
Ion beam epitaxy provided by the invention (IBE) growth apparatus prepares the method and thin film material of metal zirconium preparation method commonly used at present of thin film material of metal zirconium, as magnetron sputtering, pulsed laser deposition (PLD), ion beam assisted depositing (IBAD), electron beam evaporations etc. are compared, method of the present invention can make raw-material purification, the preparation of thin-film material is grown in same process and finishes under the cleaning of substrate and the ultrahigh vacuum(HHV), utilize starting material cheaply to realize the high-purity high-quality growth and the low-temperature epitaxy of metal zirconium film, and growth technique is convenient to regulation and control and is optimized, and is the difficulty purification that a kind of economical and practical preparation is applied to technical field of semiconductors, the method of refractory metal zirconium thin-film material.
Description of drawings
Fig. 1: prepare the method for thin film material of metal zirconium for the present invention is a kind of, ion beam epitaxy (IBE) the growth apparatus synoptic diagram of preparation thin film material of metal zirconium;
Fig. 2. on silicon Si (111) substrate, utilize X-ray diffraction (XRD) spectrum of the metal zirconium film sample that ion beam epitaxy (IBE) growth apparatus prepares;
Fig. 3. on silicon Si (111) substrate, utilize atomic power surface topography (AFM) figure of the metal zirconium film sample that ion beam epitaxy (IBE) growth apparatus prepares;
Fig. 4. on silicon Si (111) substrate, utilize the x-ray photoelectron power spectrum (XPS) of the metal zirconium film sample that ion beam epitaxy (IBE) growth apparatus prepares.
Embodiment
See also shown in Figure 1, the ion beam epitaxy growth apparatus preparation that the present invention is used for thin film material of metal zirconium preparation growth has dual beam structure, I bundle and II bundle, every bundle has independently ion source 1.1 and 1.2 devices, ion source line regulation device 2, magnetic analyzer device 3, electric or magnetic quadrupole lens device 5.1 and 5.2, electrostatic deflection electrodes device 6, and shared retarding lens device 7, silicon substrate 8 and the ion beam flow measuring apparatus 9 of two-beam is positioned at ultrahigh vacuum(HHV) growth room 10.The vacuum of total system adopts the design of difference bleeder, and the vacuum of installing growth room's (target chamber) 10 from ion source 1.1 and 1.2 improves one by one, and the base vacuum of growth room 10 can be up to 2 * 10
-7Pa.
Be used for the argon (Ar that the silicon substrate dry method is cleaned
+) ionic fluid 4.2 or be used for the nitrogen ion (N of thin zirconium nitride buffer layer preparation growth
+) bundle 4.2 and zirconium (Zr
+) step that comprises of the generation of ionic fluid 4.1 and the preparation process of growth of thin film material of metal zirconium is as follows:
Step 1: select the starting material of the not high low-cost zirconium chloride pressed powder of purity requirement for use as the Bai Nasi type solid ion source 1.1 generation zirconium ion bundles of ion beam epitaxy growth apparatus I bundle, and in the evaporator type crucible with its Bai Nasi type solid ion source 1.1 devices of packing into;
Step 2: select for use argon gas to produce the starting material of the ar-ion beam that is used for the cleaning of substrate surface dry method as the Bai Nasi type gas ion source 1.2 of ion beam epitaxy growth apparatus II bundle;
Step 3: select for use nitrogen to produce the nitrogen ion beam starting material that are used for the thin buffer layer of the long zirconium nitride of zirconium ion fasciculation symphysis as the Bai Nasi type gas ion source 1.2 of ion beam epitaxy growth apparatus II bundle;
Step 4: will clean with the silicon substrate 8 of deoxidation layer and insert in the growth room 10;
Step 5: the vacuum that detaches sub-beam epitaxy growth apparatus;
Step 6: in ion source vacuum reach≤10
-4Pa begins baking and degass, and Bai Nasi type solid ion source 1.1 devices of I bundle can be controlled the temperature of baking heating by adjusting its filament heating current, crucible heating current and arc chamber heating current, and the storing temperature that this ion source baking is degassed is 120～140 ℃.Bai Nasi type gas ion source 1.2 devices of II bundle are controlled the temperature of baking heating by adjusting its filament heating current, and the baking Heating temperature is more than 120 ℃;
Step 7: the vacuum tightness in growth room 10 reaches 10
-7Behind the Pa, the baking that begins to carry out silicon substrate 8 is degassed and the high temperature deoxidation treatment, and substrate 8 is heated to 800 ℃, continues to cool to room temperature naturally after 30 minutes;
Step 8: it is as follows to utilize the II bundle of ion beam epitaxy growth apparatus to produce the detailed process of high-energy argon ion bundle 4.2 of isotopic pure:
1) vacuum tightness after the 1.2 device bakings of II bundle Bai Nasi type gas ion source are degassed reaches 10
-4Behind the Pa, the container of splendid attire argon gas is connected with the Bai Nasi type gas ion source 1.2 devices air-intake duct outward of ion beam epitaxy growth apparatus II bundle, and in ion source 1.2 logical argon gas, the flow of air inlet is gone up noticeable degree by it, to keep the interior air pressure of this ion source 1.2 1.5 * 10
-3Be as the criterion about Pa;
2) add the acceleration voltage of ion beam epitaxy growth apparatus work, add the arc chamber voltage of ion source 1.2 and draw focusing electrode voltage, rise source field supply and filament heating current, make the atmosphere starting the arc that enters the intravital argon gas of ion source 1.2 arc chambers, ionization goes out argon ion, after the acceleration voltage of ion beam system work quickens to be shaped, draw ionic fluid by the negative high voltage electric field action of drawing focusing electrode, adjust filament heating current and source field supply and control the arc stream size of generation, and make ion source 1.2 stably produce the ion beam current that contains argon ion in a large number, the energy region of the ionic fluid that produces is 15 to 40KeV, acceleration voltage decision when size is worked by the ion beam epitaxy growth apparatus, the operating air pressure scope of ion source 1.2 is generally 0.8 * 10
-3Pa to 4.0 * 10
-3Pa, the arc chamber range of current of ion source 1.2 steady operations be 0.5A to 3A, the big I of the ion beam current density of generation by changing ion source 1.2 work air pressure and adjust the arc stream size that produces and control;
3) high energy ion beam that generates with 3 pairs of ion sources of the magnetic analyzer device on the II bundle separates according to total mass number, selects the high-energy argon ion bundle of isotopic pure;
4) the isotopic pure high-energy argon ion Shu Jinhang secondary focusing that mass separation is obtained with the magnetic quadrupole lens device 5.2 on the II bundle;
5) obtain isotopic pure high-energy argon ion bundle after with the electrostatic deflection electrodes device 6 on the II bundle high energy neutral particle being removed in the isotopic pure high-energy argon ion beam steering after the secondary focusing;
Step 9: open vacuum isolating valve between the ultrahigh vacuum(HHV) growth room 10 of ion beam epitaxy growth apparatus and the double-ion beam meet, the high-energy argon ion bundle vertical incidence of isotopic pure is advanced in the retarding lens device 7 in the ultrahigh vacuum(HHV) growth room 10, is 100 μ A/cm with decelerating to 300eV, bundle spot size covering entire substrate 8, beam current density
2Isotopic pure low energy ion beam bundle bombardment sputtered silicon substrate 8 surfaces, carry out dry method and clean the residual impurity of removing the substrate surface pickup, scavenging period is 2 minutes;
Rapid 10: the ar-ion beam 4.2 of closing ion beam epitaxy growth apparatus II bundle, the dry method that stops silicon substrate 8 is cleaned, close the growth room 10 of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, close the needle-valve and the argon gas of Bai Nasi type gas ion source 1.2 device external admission conduits;
Step 11: it is as follows to utilize the II bundle of ion beam epitaxy growth apparatus to produce the detailed process of high energy nitrogen ion beam 4.2 of isotopic pure:
1) vacuum tightness when II bundle Bai Nasi type gas ion source 1.2 reaches 10
-4Behind the Pa, the container of splendid attire nitrogen is connected with the Bai Nasi type gas ion source 1.2 devices air-intake duct outward of ion beam epitaxy growth apparatus II bundle, and in ion source 1.2 logical nitrogen, the flow of air inlet is gone up noticeable degree by it, to keep the interior air pressure of this ion source 1.2 1.5 * 10
-3Be as the criterion about Pa;
2) add the acceleration voltage of ion beam epitaxy growth apparatus work, add the arc chamber voltage of ion source 1.2 and draw focusing electrode voltage, rise source field supply and filament heating current, make the atmosphere starting the arc that enters the intravital nitrogen of ion source 1.2 arc chambers, ionization goes out the nitrogen ion, after the acceleration voltage of ion beam system work quickens to be shaped, draw ionic fluid by the negative high voltage electric field action of drawing focusing electrode, adjust filament heating current and source field supply and control the arc stream size of generation, make ion source 1.2 stably produce and contain nitrogen ionic ion beam current in a large number, the energy region of the ionic fluid that produces is 15 to 40KeV, acceleration voltage decision when size is worked by the ion beam epitaxy growth apparatus, the operating air pressure scope of ion source 1.2 is generally 0.8 * 10
-3Pa to 4.0 * 10
-3Pa, the arc chamber range of current of ion source 1.2 steady operations be 0.5A to 3A, the big I of the ion beam current density of generation by changing ion source 1.2 work air pressure and adjust the arc stream size that produces and control;
3) high energy ion beam that generates with 3 pairs of ion sources of the magnetic analyzer device on the II bundle separates according to total mass number, the high energy nitrogen ion beam of the isotopic pure of selecting;
4) with the magnetic quadrupole lens device 5.2 on the II bundle isotopic pure high energy nitrogen ion beam that mass separation obtains is carried out secondary focusing;
5) obtain isotopic pure high energy nitrogen ion beam after with the electrostatic deflection electrodes device 6 on the II bundle high energy neutral particle being removed in the isotopic pure high energy nitrogen ion beam deflection after the secondary focusing;
Step 12: it is as follows to utilize the I bundle of ion beam epitaxy growth apparatus to produce the detailed process of high energy zirconium ion bundle 4.1 of isotopic pure:
1) vacuum tightness after source 1.1 bakings of I bundle Bai Nasi type solid ion are degassed reaches 10
- 4Behind the Pa, continue slow elevated temperature, make it slowly evaporate zirconium chloride atmosphere, the air pressure of the zirconium chloride atmosphere in ion source is raised to 1.5 * 10
-3During Pa, suitably reduce filament heating current, crucible heating current and arc chamber heating current, temporarily stop to continue to heat up, to keep the stable gas pressure in this ion source;
2) elder generation suitably reduces the filament heating current in Bai Nasi type solid ion source 1.1, crucible heating current and arc chamber heating current, add arc chamber voltage and focus on extraction pole voltage, rise source field supply and filament heating current, make and enter the ion that the intravital zirconium chloride atmosphere of ion source 1.1 arc chambers starting the arc ionization goes out to contain zirconium ion, the ion that ionization is come out is after the acceleration voltage of ion beam system work quickens to be shaped, draw the negative high voltage electric field action of focusing electrode by ion source and draw ionic fluid, control the arc stream size of generation by adjusting filament heating current and source field supply again, after treating that arc stream is stable, suitably increase ion source arc chamber heating current and crucible heating current, by working temperature in the regulation and control ion source, the operating air pressure of keeping the zirconium chloride atmosphere that is evaporated is stable, and makes ion source stably produce the ion beam current that contains zirconium ion in a large number.The energy region of the high energy ion beam that is generated by ion source 1.1 is 15 to 40KeV, acceleration voltage decision when size is worked by the ion beam epitaxy growth apparatus, the operating temperature range of ion source 1.1 is 150 to 300 ℃, and the operating air pressure scope of zirconium chloride atmosphere is 0.8 * 10
-3Pa to 4.0 * 10
-3Pa, the arc chamber range of current of steady operation be 0.5A to 3A, the big I of the ion beam current density of generation causes that by working temperature in the change source operating air pressure of zirconium chloride atmosphere changes and adjusts the arc stream size that produces and control;
3) high energy ion beam that generates with 3 pairs of ion sources of the magnetic analyzer device on the I bundle separates according to total mass number, the zirconium ion bundle of the isotopic pure of selecting;
4) the isotopic pure high energy zirconium ion Shu Jinhang secondary focusing that mass separation is obtained with the electric quadrupole lens devices 5.1 on the I bundle;
5) obtain isotopic pure high energy zirconium ion bundle 4.1 after with the electrostatic deflection electrodes device 6 on the I bundle high energy neutral particle being removed in the isotopic pure high energy zirconium ion beam steering after the secondary focusing.
Step 13: the low energy zirconium ion bundle 4.1 of the isotopic pure that the ion beam epitaxy growth apparatus produces and the thin zirconium nitride buffer layer of nitrogen ion beam 4.2 alternating deposit chemical combination growth, detailed process is as follows:
1) opens the growth room 10 of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, under the timesharing cutting conducting effect of the ion source line regulation device 2 on two bundles, the high energy zirconium ion bundle 4.1 of isotopic pure and nitrogen ion beam 4.2 vertical incidence are alternately advanced in the retarding lens device 7 in the ultrahigh vacuum(HHV) growth room 10, and slowing down obtains isotopic pure low energy zirconium ion bundle and the nitrogen ion beam of 200eV;
2) the electric quadrupole lens devices 5.1 and the electric field of auxiliary electric liner, magnetic quadrupole lens device 5.2 and the magnetic field of auxiliary magnetic steering device and the electric field of electrostatic deflection electrodes device 6 of II bundle by readjusting the I bundle, make alternating deposit cover entire substrate, and big or small same position overlap to the two bundle spots of restrainting the low energy ion of isotopic pures on the substrate;
3) zirconium ion of setting according to ion beam flow measuring apparatus 9: the proportioning of nitrogen ion=1: 4, with each cycle deposition 6.25 * 10
14The zirconium ion of dose and 25.00 * 10
14The nitrogen ionic dosage of dose, on silicon substrate 8, the thin zirconium nitride buffer layer of preparation growth one deck, the cycle count of alternating deposit growth is 50, vacuum tightness≤5.0 * 10 in the ultrahigh vacuum(HHV) growth room 10 in the process of growth
-6Pa, substrate heating temperature are 300 ℃, and utilize the scanning that swings of the Small angle of substrate, further improve the thin epitaxially grown homogeneity of zirconium nitride buffer layer.
Step 14: close the nitrogen ion beam 4.2 of ion beam epitaxy growth apparatus II bundle, the air inlet needle-valve and the nitrogen of the Bai Nasi type gas ion source 1.2 of II bundle are closed in the epitaxy of the zirconium buffer layer that stops nitride;
Step 15: the I bundle with the ion beam epitaxy growth apparatus produces isotopic pure zirconium ion bundle 4.1 separately, with lower 200eV ion energy, on thin zirconium nitride buffer layer, the epitaxy thin film material of metal zirconium, in process of growth, vacuum tightness in the ultrahigh vacuum(HHV) growth room 10≤5.0 * 10
-6Pa, substrate heating temperature are 300 ℃, and utilize the scanning that swings of the Small angle of substrate, further improve the homogeneity of metal zirconium thin film epitaxial growth.
Realize best way of the present invention:
1, realize the major equipment of invention:
The cleaning equipment of ion beam epitaxy growth apparatus, vacuum apparatus (oil-sealed rotary pump, turbomolecular pump, cryopump, ionic pump etc.), semiconductor substrate materials etc.;
2. according to the particular case of growth apparatus and the requirement of the metal zirconium film that will prepare, design the technological line of enforcement of the present invention.
Embodiment
Specific embodiment sees Table 1 related experiment data and Fig. 2,3,4 experimental result.
Table 1: on the silicon Si substrate, utilize ion beam epitaxy (IBE) growth apparatus to prepare the experiment parameter and the result of thin film material of metal zirconium.
Fig. 2. on silicon Si (111) substrate, utilize X-ray diffraction (XRD) spectrum of the metal zirconium film sample that (IBE) growth apparatus prepares outside the ionic fluid: test result shows that the film sample for preparing has single-orientated high crystalline quality growth.
Fig. 3. on silicon Si (111) substrate, utilize atomic power surface topography (AFM) figure of the metal zirconium film sample that (IBE) growth apparatus prepares outside the ionic fluid: sample is at 5 * 5 μ m
2R.m.s. roughness (RMS) in the yardstick is 1.40nm, shows that the metal zirconium film sample surface smoother for preparing is smooth.
Fig. 4. on silicon Si (111) substrate, utilize the x-ray photoelectron power spectrum (XPS) of the metal zirconium film sample that ion beam epitaxy (IBE) growth apparatus prepares: test result shows that sample has the chemical structure state of metal zirconium, and the Ols peak in the full spectrum is oxygen impurities and the partial oxidation that there be absorption in the sample surface, and the Cls peak is the carbon impurity of sample surface adsorption.
Claims (16)
1. method for preparing thin film material of metal zirconium, it is characterized in that, utilization has the double-ion beam epitaxial growth equipment of mass separation function and energetic ion sedimentary characteristic, with purity is that 98.5% zirconium chloride is starting material, as the starting material that produce the zirconium ion bundle, on the clean silicon substrate of crossing with the isotopic pure low energy ion beam bombardment sputter clean of Dan Shu, prepare the thin zirconium nitride of one deck as the blocking layer and the buffer layer that stop silicon and zirconium ion generation surface reaction with isotopic pure low energy metal zirconium ionic fluid that produces and nitrogen ion beam earlier, use the isotopic pure low energy metal zirconium ion epitaxy metal zirconium film of Dan Shu again, energy by accurate control zirconium ion bundle, deposit dose, beam current density, bundle shape of spot and growth temperature, in the ultrahigh vacuum(HHV) growth room, realize difficult the purification, refractory metal zirconium film low-cost high-purity, high crystalline quality growth and low-temperature epitaxy.
2. the method for preparing thin film material of metal zirconium according to claim 1 is meant a kind of double-ion beam epitaxial growth equipment that utilizes, and on substrate, prepares the method for difficult purification, high-melting point metal zirconium thin-film material, it is characterized in that, comprises the steps:
Step 1: to select purity for use be 98.5% low-cost zirconium chloride pressed powder produces the starting material of zirconium ion bundle as the Bai Nasi type solid ion source of ion beam epitaxy growth apparatus I bundle, and in the evaporator type crucible with its Bai Nasi type solid ion source apparatus of packing into;
Step 2: select for use argon gas to produce the starting material of the ar-ion beam that is used for the cleaning of substrate surface dry method as the Bai Nasi type gas ion source of ion beam epitaxy growth apparatus II bundle;
Step 3: select for use nitrogen to be used for and the long starting material that approach the nitrogen ion beam of zirconium nitride buffer layer of zirconium ion fasciculation symphysis as the Bai Nasi type gas ion source generation of ion beam epitaxy growth apparatus II bundle;
Step 4: the substrate that will clean is inserted the growth room;
Step 5: the vacuum that detaches sub-beam epitaxy growth apparatus;
Step 6: two ion source bakings to the ion beam epitaxy growth apparatus are degassed;
Step 7: baking is degassed or is carried out the high temperature deoxidation treatment to the substrate in the growth room;
Step 8: the air-intake duct that the container and the Bai Nasi type gaseous ion source apparatus of ion beam epitaxy growth apparatus II bundle of splendid attire argon gas is outer is connected, by the noticeable degree charge flow rate on it, logical argon gas in ion source, and utilize double-ion beam epitaxial growth equipment II bundle to produce the high-energy argon ion bundle of isotopic pure;
Step 9: open the ultrahigh vacuum(HHV) growth room of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, the high-energy argon ion bundle vertical incidence of isotopic pure is advanced in the retarding lens device in the ultrahigh vacuum(HHV) growth room, isotopic pure low energy ion beam bundle bombardment sputter substrate surface with deceleration obtains carries out the residual impurity that dry method is cleaned the substrate surface pickup;
Step 10: the ar-ion beam of closing ion beam epitaxy growth apparatus II bundle, the dry method that stops substrate being cleaned, close the vacuum isolating valve between ion beam epitaxy growth apparatus growth room and the double-ion beam meet, close Bai Nasi type gaseous ion source apparatus external admission conduit needle-valve and argon gas;
Step 11: the container of splendid attire nitrogen is connected with the Bai Nasi type gaseous ion source apparatus external admission conduit of ion beam epitaxy growth apparatus II bundle, by the noticeable degree charge flow rate on it, logical nitrogen in ion source utilizes double-ion beam epitaxial growth equipment I I bundle to produce the high energy nitrogen ion beam of isotopic pure;
Step 12: the temperature after the Bai Nasi type solid ion source apparatus baking that continues slow rising I bundle is degassed, make it slowly evaporate zirconium chloride atmosphere, by the working temperature in the control ion source, it is stable to keep its operating air pressure, and utilizes double-ion beam epitaxial growth equipment I bundle to produce the high energy zirconium ion bundle of isotopic pure;
Step 13: open the growth room of ion beam epitaxy growth apparatus and the vacuum isolating valve between the double-ion beam meet, utilize the timesharing cutting conducting function of ion source line regulation device, make the high energy zirconium ion bundle of isotopic pure and nitrogen ion beam alternately vertical incidence advance in the retarding lens device in the ultrahigh vacuum(HHV) growth room, the isotopic pure low energy zirconium ion bundle and the nitrogen ion beam that slow down and obtain, the dosage and the proportioning of the cycle alternating deposit of setting according to the ion beam flow measuring apparatus, the thin zirconium nitride layer of preparation growth one deck is as stopping the blocking layer of substrate material and zirconium ion generation surface reaction and the buffer layer of growing metal zirconium film on substrate;
Step 14: close the nitrogen ion beam of ion beam epitaxy growth apparatus II bundle, stop the epitaxy of thin zirconium nitride buffer layer, close the air inlet needle-valve and the nitrogen of the Bai Nasi type gas ion source of II bundle;
Step 15: restraint the isotopic pure zirconium ion bundle that produces with ion beam epitaxy growth apparatus I separately, in the ultrahigh vacuum(HHV) growth room, with lower energy, epitaxy thin film material of metal zirconium on thin zirconium nitride buffer layer.
3. the method for preparing thin film material of metal zirconium according to claim 2 is characterized in that, vacuum tightness≤10 in the ion source before the baking in the described step 6 is degassed
-4Pa, the temperature of baking heating is controlled by adjusting its filament heating current, crucible heating current and arc chamber heating current in the Bai Nasi type solid ion source of I bundle, the temperature of this ion source baking heating is 120-140 ℃, the Bai Nasi type gas ion source of II bundle is controlled the temperature of baking heating by adjusting its filament heating current, and the baking Heating temperature is 〉=120 ℃.
4. the method for preparing thin film material of metal zirconium according to claim 2 is characterized in that, before the baking of substrate in the described step 7 is degassed the indoor vacuum tightness of growth should reach≤5 * 10
-6Pa by the Heating temperature that lining heat provides substrate baking to degas, degass or needs the temperature and time of high temperature deoxidation treatment, and according to the difference of substrate type and difference, maximum heating temperature is 800 ℃.
5. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the energy region of the described isotopic pure low energy ion beam that is used for substrate surface bombardment sputter clean in carry out step 9 is 100 to 1KeV, and beam current density is 50 to 100 μ A/cm
2, bundle spot size covers entire substrate, determines energy, beam current density and the scavenging period of the low energy ion beam that is used for cleaning according to the substrate type difference.
6. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the low energy zirconium ion bundle and the nitrogen ion beam of the described isotopic pure that obtains after slowing down in carry out step 13, by the electric quadrupole lens devices and the electric field of auxiliary electric liner, magnetic quadrupole lens device and the magnetic field of auxiliary magnetic steering device and the electric field of electrostatic deflection electrodes device that II restraints of readjusting I bundle, make alternating deposit cover entire substrate, and big or small same position overlap to the two bundle spots of restrainting the low energy ion beam of isotopic pures on the substrate.
7. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the energy region that described being used in carry out step 13 prepares the isotopic pure zirconium ion bundle of the thin zirconium nitride buffer layer of growth and nitrogen ion beam after slowing down is 15 to 1KeV, according to substrate type difference and the growth needs that growth is adopted, determine energy, beam current density and the alternating deposit dosage and the proportioning of the low energy ion of participation growth.
8. the method for preparing thin film material of metal zirconium according to claim 2 is characterized in that, described carry out step 13 in the time vacuum tightness≤5.0 * 10 in the ultrahigh vacuum(HHV) growth room
-6Pa, the preparation growth temperature of thin zirconium nitride buffer layer is provided by lining heat, and the intensification scope is a room temperature to 800 ℃, and the substrate type that is adopted according to growth is different and growth needs is definite.
9. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, described carry out step 13 in the time, in process of growth, the scanning that swings of Small angle by substrate further improves the thin epitaxially grown homogeneity of zirconium nitride buffer layer.
10. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the energy region that described being used in carry out step 15 prepares the isotopic pure low energy zirconium ion of growing metal zirconium film be 15eV to 1KeV, can be according to the substrate type that growth be adopted different and growth needs is definite.
11. the method for preparing thin film material of metal zirconium according to claim 2 is characterized in that, described carry out step 15 in the time vacuum tightness≤5 * 10 in the ultrahigh vacuum(HHV) growth room
-6Pa, preparation growing metal zirconium growth for Thin Film temperature is provided by lining heat, and the intensification scope is a room temperature to 800 ℃, and the substrate type that is adopted according to growth is different and growth needs is definite.
12. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the preparation growth of described metal zirconium film in carry out step 15, the scanning that can swing by the Small angle of substrate further improves the homogeneity of metal zirconium thin film epitaxial growth.
13. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the preparation growth of described metal zirconium film in carry out step 15, bundle spot size that can be by adjusting epitaxially grown low energy metal zirconium ionic fluid and sedimentary dosage come the area and the thickness of the metal zirconium film that control growing obtains.
14. the method for preparing thin film material of metal zirconium according to claim 1 and 2 is characterized in that, in vacuum tightness≤5 * 10
-6In the ultrahigh vacuum(HHV) growth room of Pa, adopt silicon as substrate, after substrate cleans through the isotopic pure low energy ion beam bundle bombardment sputter dry method of 300eV, underlayer temperature with 295 ℃～305 ℃, earlier with the 200eV isotopic pure low energy metal zirconium ionic fluid and the nitrogen ion beam that produce, alternating deposit prepares the thin zirconium nitride of one deck as the blocking layer and the buffer layer that stop silicon substrate and zirconium ion generation surface reaction, use the 200eV isotopic pure low energy metal zirconium ion epitaxy of Dan Shu again, prepare and have high crystalline quality metal zirconium film highly single-orientated and that smooth surface is smooth.
15. the method for preparing thin film material of metal zirconium according to claim 14 is characterized in that, wherein, the beam current density that is used for the low energy ion beam bundle of silicon substrate dry method cleaning is 100 μ A/cm
2, scavenging period is 2～3 minutes.
16. the method for preparing thin film material of metal zirconium according to claim 14 is characterized in that, wherein, the dosage that is used for alternating deposit in single cycle of the isotopic pure low energy zirconium ion bundle of thin zirconium nitride buffer layer preparation and nitrogen ion beam is 6.25 * 10
14Dose and 25.00 * 10
14Dose, total cycle count is 50, zirconium ion is 1 to 4 with nitrogen ionic deposit dose ratio.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4179312A (en) * | 1977-12-08 | 1979-12-18 | International Business Machines Corporation | Formation of epitaxial layers doped with conductivity-determining impurities by ion deposition |
| CN1308145A (en) * | 2000-11-17 | 2001-08-15 | 武汉大学 | Gallium nitride film preparing technology and special equipment |
| CN1353442A (en) * | 2000-11-10 | 2002-06-12 | 日新电机株式会社 | Apparatus and method for producing indium ion beam |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4179312A (en) * | 1977-12-08 | 1979-12-18 | International Business Machines Corporation | Formation of epitaxial layers doped with conductivity-determining impurities by ion deposition |
| CN1353442A (en) * | 2000-11-10 | 2002-06-12 | 日新电机株式会社 | Apparatus and method for producing indium ion beam |
| CN1308145A (en) * | 2000-11-17 | 2001-08-15 | 武汉大学 | Gallium nitride film preparing technology and special equipment |
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| IBE双离子束外延实验机. 李景春.电子工业专用设备，第4期. 1988 * |
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