CN1796596A - 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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Abstract
This invention provides a preparation method for zirconium thin films. A dual ion beam epitaxy apparatus with the function of mass separation and characteristics of energetic ion deposition is adopted and zirconium chloride of which purity is not highly required serves as raw materials and is sputtered to a sanitized substrate with single isotopic pure low-energy argon ion beam. First, a thin film of zirconium nitride as block layer and buffer layer preventing reactions between zirconium ion and the substrate is prepared with the consequent isotopic pure low-energy zirconium ion beam and nitrogen ion beam, and then a zirconium film is deposited by epitaxy of single isotopic pure low-energy zirconium ion beam. By exactly controlling the energy of zirconium ion beam, the amount of deposition agents, beam density, beam shape and growing temperature, low-cost deposition and low-temperature epitaxy of zirconium which has a high melting point and is difficult to purify can be realized in ultravacuum cultivation room with high purity and high crystallization quality. This technique is convenient to modulate and optimized and is economical to manufacture zirconium thin films.
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, dystectic metal zirconium (Zr) thin-film material.
Background technology
IVB family refractory metal zirconium (Zr) is as 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, so that device feature size constantly reduces, 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 of zirconium, nitride and metallic film can be expected to become the ideal candidates material that following microelectric technique this respect needs. And with regard to the metallic film of zirconium (Zr), because it has good heat endurance (fusing point is 1930 ℃), strong anticorrosion properties, good electric conductivity (room temperature resistivity is 40 μ Ω .cm) and and silicon (Si) between less lattice mismatch (0.967%) and thermal expansion coefficient difference are arranged, get a good chance of becoming the same important meals thin-film material of Titanium film of commonly using with present technical field of semiconductors, and at high temperature, high frequency, application on the microelectronic component 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 paprmeter of metal zirconium film, thermal coefficient of expansion and important third generation compound semiconductor materials--gallium nitride (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 probably become the desirable cushioning layer material of MBE method growing GaN epitaxial loayer, although metal current zirconium (Zr) film has made 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, so that prepare 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 growing method commonly used, usually all very high to raw-material purity requirement, and the highly purified zirconium raw material that contain are than the titaniferous prices of raw and semifnished materials more expensive 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 raw material, restricted greatly metal current zirconium film and used widely and promote at semiconductor applications;
2) existing preparation growing method commonly used, its growth course usually all be have back work gas than the low vacuum environment under grow, so be unfavorable for obtaining film high-purity, high crystalline quality. The impurity particularly introducing of oxygen can reduce crystalline quality and the electrical conductivity of film, and then affects device performance;
3) existing preparation growing method commonly used, its growth temperature is usually all higher, in the starting stage of growth, forming at the interface silicide or other intermediate compounds possibly, and increase contact resistance and affect the quality that subsequent thin film is grown, needing low underlayer temperature (below 560 ℃), also is the requirement of present microelectric technique;
4) existing preparation growing method commonly used, the aspects such as flatness of internal stress, raising film surface are also not fully up to expectations in reducing metal zirconium film rete. Surface undulation is unfavorable for greatly the carrying out of secondary epitaxy and subsequent technique, and is poor and leakage current is large such as the large blocking effect of pinhold density, and the mechanical property of film is bad also may to be affected subsequent technique and carry out serviceability 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 ripe 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, sometimes also claims the low energy ion beam deposition of mass separation. Because it has unique mass separation function and energetic ion sedimentary characteristic, can be so that the purification of material and thin film epitaxial growth be finished 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 the method adopts, its ion beam part has dual beam structure usually, every bundle has the independently devices such as ion gun, magnetic analyzer, electric or magnetic quadrupole lense and electrostatic deflection electrodes, the retarding lens device that two-beam shares is positioned at the growth room, the mode that the vacuum design of whole growing system adopts difference to bleed designs, vacuum from the ion gun to the growth room improves step by step, the dynamic vacuum degree of ultrahigh vacuum growth room≤5.0 * 10-7Pa. The ion gun of this system almost can produce the ion of mass number from 1 (H) to all elements of 208 (Pb) in the periodic table of elements, and selects to purify according to mass number by the magnetic analyzer device of this system. Not being the material ion that very high raw material can produce isotopically pure with purity, and realizing ultrapure growth and the low temperature high-quality extension of film in the ultrahigh vacuum growth room, is a large characteristic of the method. The Low energy ion beam epitaxy method of mass separation is being achieved success aspect the growth preparation research of rare earth films material at present, but the increment study that utilizes the 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, dystectic metal zirconium (Zr) thin-film material. Purpose is to reduce the preparation cost of metal zirconium (Zr) thin-film material, realize that it is high-purity, the growth of the high-quality of high crystalline quality and low-temperature epitaxy, develop 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 adopts 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, take the not high low-cost zirconium chloride of purity requirement as raw material, on the clean silicon substrate of crossing with the isotopically pure low energy ion beam bombardment sputter clean of Dan Shu, prepare the thin zirconium nitride of one deck as the barrier layer and the cushion that stop silicon and zirconium ion generation interfacial reaction with the isotopically pure low energy metal zirconium ion beam that produces and nitrogen ion beam first, use again the isotopically pure low energy metal zirconium ion epitaxial growth metal zirconium film of Dan Shu, energy, deposit dose, beam current density, bundle shape of spot and growth temperature by accurate control zirconium ion bundle, in the ultrahigh vacuum growth room, realize low-cost high-purity, high crystalline quality growth and the low-temperature epitaxy of difficult purification, refractory metal zirconium film.
The described method for preparing thin film material of metal zirconium refers to a kind of ion beam epitaxy growth apparatus that utilizes especially, on substrate, prepares the method for difficult purification, dystectic thin film material of metal zirconium, comprises the steps:
Step 1: select the not high low-cost zirconium chloride pressed powder of purity requirement as the raw material of 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 argon gas to produce the raw 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 nitrogen to produce the raw material that are used for growing with the symphysis of zirconium ion fasciculation the nitrogen ion beam of thin zirconium nitride cushion as the Bai Nasi type gas ion source 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 gun 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 induction conduit that container and the Bai Nasi type gas ion source device 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, in ion gun, lead to argon gas, and utilize this ion beam to produce the high-energy argon ion bundle of isotopically pure;
Step 9: open the ultrahigh vacuum 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 isotopically pure is advanced in the retarding lens device in the ultrahigh vacuum growth room, isotopically 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 needle-valve and the argon gas of Bai Nasi type gas ion source device external admission conduit;
Step 11: the container of splendid attire nitrogen is connected with the Bai Nasi type gas ion source device external admission conduit of ion beam epitaxy growth apparatus II bundle, by the noticeable degree charge flow rate on it, in ion gun, lead to nitrogen, utilize this ion beam to produce the high energy nitrogen ion beam of isotopically pure;
Step 12: the temperature after the Bai Nasi type solid ion source apparatus baking that continues slow rising I bundle is degassed, make its slow evaporation go out zirconium chloride atmosphere, by the operating temperature in the control ion gun, it is stable to keep its operating air pressure, and utilizes this ion beam to produce the high energy zirconium ion bundle of isotopically 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 gun line regulation device, the high energy zirconium ion bundle of isotopically pure and nitrogen ion beam vertical incidence are alternately advanced in the retarding lens device in the ultrahigh vacuum growth room, the isotopically pure low energy zirconium ion bundle and the nitrogen ion beam that slow down and obtain, dosage and the proportioning of the cycle alternating deposit of setting according to the ion beam flow measuring apparatus, in the thin zirconium nitride layer of substrate preparation growth one deck as stopping the barrier layer of backing material and zirconium ion generation interfacial reaction and the cushion of growing metal zirconium film;
Step 14: close the nitrogen ion beam of ion beam epitaxy growth apparatus II bundle, stop the epitaxial growth of thin zirconium nitride cushion, close air inlet needle-valve and the nitrogen of the Bai Nasi type gas ion source of II bundle;
Step 15: the isotopically pure zirconium ion bundle that produces with ion beam epitaxy growth apparatus I bundle separately, in the ultrahigh vacuum growth room, with lower energy, epitaxial growth thin film material of metal zirconium on thin zirconium nitride cushion.
Vacuum in the ion gun 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 out is controlled in the Bai Nasi type solid ion source of I bundle by adjusting its filament heating electric current, crucible heating electric current and arc chamber heating current, the temperature of this ion gun Baking out is 120～140 ℃, the Bai Nasi type gas ion source of II bundle is controlled the temperature of Baking out by adjusting its filament heating electric current, the Baking out temperature is 〉=120 ℃.
The described method for preparing thin film material of metal zirconium, the baking of substrate in its described step 7 degas the indoor vacuum of front growth should reach≤5 * 10-6Pa by the heating-up 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 range of the isotopically 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/cm2, bundle spot size covers whole substrate, energy, beam current density and the scavenging period of the low energy ion beam of determining to clean according to the substrate type difference.
The described method for preparing thin film material of metal zirconium, low energy zirconium ion bundle and the nitrogen ion beam of the isotopically pure that it is described to obtain after slowing down in carry out step 13, by the electric field of readjusting I the electric quadrupole lens devices of restrainting and the electric guider of assisting, magnetic quadrupole lens device and the magnetic field of the magnetic steering device of assisting and the electric field of electrostatic deflection electrodes device of II bundle, so that alternating deposit covers whole substrate to the two bundle spots of restrainting the low energy ion beam of isotopically pures on the substrate, and big or small same position overlaps.
The described method for preparing thin film material of metal zirconium, the energy range that it is described in carry out step 13 for the preparation of the isotopically pure zirconium ion bundle of the thin zirconium nitride cushion 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 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≤5.0 * 10 in the ultrahigh vacuum growth room-6Pa, the preparation growth temperature of thin zirconium nitride cushion is provided by lining heat, and the intensification scope is room temperature to 800 ℃, and the substrate type that adopts 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 growth course, the scanning that swings of the low-angle by substrate further improves the epitaxially grown uniformity of thin zirconium nitride cushion.
The described method for preparing thin film material of metal zirconium, it is described in carry out step 15 for the preparation of the energy range of the isotopically 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≤5 * 10 in the ultrahigh vacuum growth room-6Pa, the growth temperature of preparation growing metal zirconium film is provided by lining heat, and the intensification scope is room temperature to 800 ℃, and the substrate type that adopts according to growth is different and growth needs is definite.
The described method for preparing thin film material of metal zirconium, the metal zirconium thin film technology growth that it is described in carry out step 15, the scanning that can swing by the low-angle of substrate further improves the uniformity of metal zirconium thin film epitaxial growth.
The described method for preparing thin film material of metal zirconium, area and the thickness of the metal zirconium film that growth obtains is controlled in the metal zirconium thin film technology growth that it is described in carry out step 15, bundle spot size that can be by adjusting epitaxially grown low energy metal zirconium ion beam and the dosage of deposition.
The described method for preparing thin film material of metal zirconium, it is in vacuum≤5 * 10-6In the ultrahigh vacuum growth room of Pa, adopt silicon as substrate, after substrate cleans through the isotopically pure low energy ion beam bundle bombardment sputter dry method of 300eV, underlayer temperature with 295 ℃～305 ℃, first with the 200eV isotopically pure low energy metal zirconium ion beam and the nitrogen ion beam that produce, alternating deposit prepares the thin zirconium nitride of one deck as the barrier layer and the cushion that stop silicon substrate and zirconium ion generation interfacial reaction, use again the 200eV isotopically pure low energy metal zirconium ion epitaxial growth of Dan Shu, 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/cm2, 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 isotopically pure low energy zirconium ion bundle of thin zirconium nitride cushion preparation and nitrogen ion beam is 6.25 * 1014Dose and 25.00 * 1014Dose, total cycle count is 50, zirconium ion is 1 to 4 with the deposit dose ratio of nitrogen ion.
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 isotopically pure, in the ultrahigh vacuum growth room, carrying out the dry method of substrate cleans, can thoroughly remove the residual impurity of substrate pickup, carry out the epitaxial growth 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 first growth and metal zirconium film mismatch is as the cushion that stops that interfacial reaction barrier layer between zirconium ion and substrate and epitaxial growth are used, and is beneficial to realize that the high crystalline quality of metal zirconium film grows;
Utilize unique qualities separation function and the ion retardation function of ion beam epitaxy growth apparatus, select the not high zirconium chloride (ZrCl of purity requirement4) pressed powder and nitrogen is respectively as producing isotopically pure low energy metal zirconium ion (Zr+) bundle and nitrogen ion (N+) bundle raw material, reduced the cost of raw material of thin zirconium nitride (ZrN) cushion and metal zirconium film preparation growth, and in the ultrahigh vacuum growth room without any back work gas, carry out the preparation growth of thin-film material, realized the high pure growth of the metal zirconium film of difficult purification;
Be used for carrying out the isotopically 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 local heat effect, has realized the low-temperature epitaxy of thin zirconium nitride (ZrN) cushion and metal zirconium film;
Be used for carrying out the atomic state isotopically pure low energy metal zirconium ion (Zr of thin-film material preparation growth+) and nitrogen ion (N+), has better chemism and with electric charge, can come Optimal Growing technique by deposit dose or proportioning, ion energy, ion beam spot shape and the growth temperature of accurate control and participate in growth ion, and then obtain to have the thin zirconium nitride of positive stoicheiometry (ZrN) cushion 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 for thin film material of metal zirconium and thin film material of metal zirconium preparation method commonly used at present, compare such as magnetron sputtering, pulsed laser deposition (PLD), ion beam assisted depositing (IBAD), electron beam evaporation etc., method of the present invention can make under the cleaning of raw-material purification, substrate and the ultrahigh vacuum preparation of thin-film material be grown in same process and finish, utilize raw material cheaply to realize 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 that a kind of economical and practical Application and preparation is in the difficulty purification of technical field of semiconductors, the method for 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 schematic 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 force 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.
The specific 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 gun 1.1 and 1.2 devices, ion gun line regulation device 2, magnetic analyzer device 3, electric or magnetic quadrupole lense device 5.1 and 5.2, electrostatic deflection electrodes device 6, and retarding lens device 7, silicon substrate 8 and ion beam flow measuring apparatus 9 that two-beam shares are positioned at ultrahigh vacuum growth room 10. The vacuum of whole system adopts the design of difference bleeder, and the vacuum of (target chamber) 10 to the growth room improves one by one from ion gun 1.1 and 1.2 devices, 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+) ion beam 4.2 or be used for the nitrogen ion (N of thin zirconium nitride cushion preparation growth+) bundle 4.2 and zirconium (Zr+) step that comprises of the generation of ion beam 4.1 and the preparation growth course of thin film material of metal zirconium is as follows:
Step 1: select the not high low-cost zirconium chloride pressed powder of purity requirement as the raw material of 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 argon gas to produce the raw 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 nitrogen to produce the nitrogen ion beam raw material that are used for the thin cushion 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 gun vacuum reach≤10-4Pa, beginning baking degass, Bai Nasi type solid ion source 1.1 devices of I bundle can be controlled by adjusting its filament heating electric current, crucible heating electric current and arc chamber heating current the temperature of Baking out, and the baking temperature that this ion gun baking is degassed is 120～140 ℃. Bai Nasi type gas ion source 1.2 devices of II bundle are controlled the temperature of Baking out by adjusting its filament heating electric current, the Baking out temperature is more than 120 ℃;
Step 7: the vacuum 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 naturally to cool to room temperature 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 isotopically pure:
1) vacuum 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 induction conduit outward of ion beam epitaxy growth apparatus II bundle, and to ion gun 1.2 interior logical argon gas, the flow of air inlet is by its upper noticeable degree, to keep the interior air pressure of this ion gun 1.2 1.5 * 10-3Be as the criterion about Pa;
2) add the accelerating potential of ion beam epitaxy growth apparatus work, add the arc chamber voltage of ion gun 1.2 and draw focusing electrode voltage, rise source field supply and filament heating electric current, make the atmosphere starting the arc that enters the argon gas in the ion gun 1.2 arc chamber bodies, ionization goes out argon ion, after the accelerating potential of ion beam system work accelerates to be shaped, draw ion beam by the negative high voltage electric field action of drawing focusing electrode, adjust filament heating electric current and source field supply and control the arc stream size of generation, and so that ion gun 1.2 stably produces the ion beam current that contains in a large number argon ion, the energy range of the ion beam that produces is 15 to 40KeV, accelerating potential when size is worked by the ion beam epitaxy growth apparatus determines that the operating air pressure scope of ion gun 1.2 is generally 0.8 * 10-3Pa to 4.0 * 10-3Pa, the arc chamber current range of ion gun 1.2 steady operations be 0.5A to 3A, the large I of the ion beam current density of generation by changing ion gun 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 guns of the magnetic analyzer device on the II bundle separates according to mass number, selects the high-energy argon ion bundle of isotopically pure;
4) the isotopically pure high-energy argon ion Shu Jinhang secondary focusing that with the magnetic quadrupole lens device 5.2 on the II bundle mass separation is obtained;
5) obtain isotopically 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 isotopically pure high-energy argon ion beam steering after the secondary focusing;
Step 9: open vacuum isolating valve between the ultrahigh vacuum growth room 10 of ion beam epitaxy growth apparatus and the double-ion beam meet, the high-energy argon ion bundle vertical incidence of isotopically pure is advanced in the retarding lens device 7 in the ultrahigh vacuum growth room 10, is 100 μ A/cm with decelerating to 300eV, the whole substrate 8 of bundle spot size covering, beam current density2Isotopically 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 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 isotopically pure:
1) vacuum 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 induction conduit outward of ion beam epitaxy growth apparatus II bundle, and to ion gun 1.2 interior logical nitrogen, the flow of air inlet is by its upper noticeable degree, to keep the interior air pressure of this ion gun 1.2 1.5 * 10-3Be as the criterion about Pa;
2) add the accelerating potential of ion beam epitaxy growth apparatus work, add the arc chamber voltage of ion gun 1.2 and draw focusing electrode voltage, rise source field supply and filament heating electric current, make the atmosphere starting the arc that enters the nitrogen in the ion gun 1.2 arc chamber bodies, ionization goes out the nitrogen ion, after the accelerating potential of ion beam system work accelerates to be shaped, draw ion beam by the negative high voltage electric field action of drawing focusing electrode, adjust filament heating electric current and source field supply and control the arc stream size of generation, so that ion gun 1.2 stably produces the ion beam current that contains in a large number the nitrogen ion, the energy range of the ion beam that produces is 15 to 40KeV, accelerating potential when size is worked by the ion beam epitaxy growth apparatus determines that the operating air pressure scope of ion gun 1.2 is generally 0.8 * 10-3Pa to 4.0 * 10-3Pa, the arc chamber current range of ion gun 1.2 steady operations be 0.5A to 3A, the large I of the ion beam current density of generation by changing ion gun 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 guns of the magnetic analyzer device on the II bundle separates according to mass number, the high energy nitrogen ion beam of the isotopically pure of selecting;
4) with the magnetic quadrupole lens device 5.2 on the II bundle isotopically pure high energy nitrogen ion beam that mass separation obtains is carried out secondary focusing;
5) obtain isotopically 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 isotopically 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 isotopically pure:
1) vacuum after source 1.1 bakings of I bundle Bai Nasi type solid ion are degassed reaches 10-4Behind the Pa, continue slow rising temperature, make its slow evaporation go out zirconium chloride atmosphere, the air pressure of the zirconium chloride atmosphere in ion gun is raised to 1.5 * 10-3During Pa, suitably reduce filament heating electric current, crucible heating electric current and arc chamber heating current, temporarily stop to continue to heat up, to keep the stable gas pressure in this ion gun;
2) elder generation suitably reduces filament heating electric current, crucible heating electric current and the arc chamber heating current in Bai Nasi type solid ion source 1.1, add arc chamber voltage and focus on extraction pole voltage, rise source field supply and filament heating electric current, make the zirconium chloride atmosphere starting the arc ionization that enters in the ion gun 1.1 arc chamber bodies go out to contain the ion of zirconium ion, ionization ion out is after the accelerating potential of ion beam system work accelerates to be shaped, drawn the negative high voltage electric field action of focusing electrode by ion gun and draw ion beam, control again the arc stream size of generation by adjusting filament heating electric current and source field supply, after arc stream is stable, suitably increase ion source arc chamber heating current and crucible heating electric current, by operating temperature in the regulation and control ion gun, the operating air pressure of keeping the zirconium chloride atmosphere that is evaporated is stable, and so that ion gun stably produces the ion beam current that contains in a large number zirconium ion. The energy range of the high energy ion beam that is generated by ion gun 1.1 is 15 to 40KeV, accelerating potential when size is worked by the ion beam epitaxy growth apparatus determines, the operating temperature range of ion gun 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 current range of steady operation be 0.5A to 3A, the large I of the ion beam current density of generation causes that by operating 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 guns of the magnetic analyzer device on the I bundle separates according to mass number, the zirconium ion bundle of the isotopically pure of selecting;
4) the isotopically pure high energy zirconium ion Shu Jinhang secondary focusing that with the electric quadrupole lens devices 5.1 on the I bundle mass separation is obtained;
5) obtain isotopically 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 isotopically pure high energy zirconium ion beam steering after the secondary focusing.
Step 13: the low energy zirconium ion bundle 4.1 of the isotopically pure that the ion beam epitaxy growth apparatus produces and the nitrogen ion beam 4.2 alternating deposit chemical combination thin zirconium nitride cushion of growing, 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 gun line regulation device 2 on two bundles, the high energy zirconium ion bundle 4.1 of isotopically pure and nitrogen ion beam 4.2 vertical incidence are alternately advanced in the retarding lens device 7 in the ultrahigh vacuum growth room 10, and slowing down obtains isotopically pure low energy zirconium ion bundle and the nitrogen ion beam of 200eV;
2) by the electric field of readjusting I the electric quadrupole lens devices 5.1 of restrainting and the electric guider of assisting, magnetic quadrupole lens device 5.2 and the magnetic field of the magnetic steering device of assisting and the electric field of electrostatic deflection electrodes device 6 of II bundle, so that alternating deposit covers whole substrate to the two bundle spots of restrainting the low energy ion of isotopically pures on the substrate, and big or small same position overlaps;
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 * 1014The zirconium ion of dose and 25.00 * 1014The dosage of the nitrogen ion of dose, on silicon substrate 8, the thin zirconium nitride cushion of preparation growth one deck, the cycle count of alternating deposit growth is 50,10 interior vacuum≤5.0 * 10, ultrahigh vacuum growth room in the growth course-6Pa, substrate heating temperature are 300 ℃, and utilize the scanning that swings of the low-angle of substrate, further improve the epitaxially grown uniformity of thin zirconium nitride cushion.
Step 14: close the nitrogen ion beam 4.2 of ion beam epitaxy growth apparatus II bundle, air inlet needle-valve and the nitrogen of the Bai Nasi type gas ion source 1.2 of II bundle are closed in the epitaxial growth of the zirconium cushion that stops nitride;
Step 15: the I bundle with the ion beam epitaxy growth apparatus produces isotopically pure zirconium ion bundle 4.1 separately, with lower 200eV ion energy, on thin zirconium nitride cushion, the epitaxial growth thin film material of metal zirconium, in growth course, 10 interior vacuum≤5.0 * 10, ultrahigh vacuum growth room-6Pa, substrate heating temperature are 300 ℃, and utilize the scanning that swings of the low-angle of substrate, further improve the uniformity of metal zirconium thin film epitaxial growth.
Realize best way of the present invention:
1, realize the capital equipment of invention:
The cleaning equipment of ion beam epitaxy growth apparatus, vacuum equipment (oil-sealed rotary pump, turbomolecular pump, cryogenic pump, ionic pump etc.), semiconductor substrate materials etc.;
2. according to the concrete condition of growth apparatus and the requirement of metal zirconium film to be prepared, design the technology path 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 experiment parameter and the result of thin film material of metal zirconium.
| V The ion beam accelerating potential | 15KV | 15KV | 15KV | ||
| V Magnetic analyzer is surveyed spectrum voltage | 362.2mV | 211.4mV | 529.4mV | ||
| I Faraday cup line behind the analyzer | 3mA | 2mA | 0.1mA | ||
| V I bundle electric quadrupole lens longitudinal voliage | 1.8KV | ||||
| V I bundle electric quadrupole lens lateral voltage | 1.5KV | ||||
| V II bundle magnetic quadrupole lens longitudinal voliage | 413mV | 218mV | |||
| V II bundle magnetic quadrupole lens lateral voltage | 341mV | 181mV | |||
| V Electrostatic deflection electrodes (positive and negative) voltage | 1.7KV | 1.6KV | 1.6KV | ||
| V Retarding lens voltage | 300V | 200V | 200V | ||
| I The target surface line | 400μA | 300μA | 30μA | ||
| Argon ion (Ar+) Shu Ganfa cleaning silicon substrate experiment parameter | |||||
| The argon ion energy | 300eV | ||||
| The ar-ion beam current density | 100μA/cm 2 | ||||
| Ar-ion |
2×2cm 2 | ||||
| The |
2 minutes | ||||
| Growth room's vacuum | ≤5×10 -6Pa | ||||
| The thin zirconium nitride cushion experiment parameter of the synthetic preparation growth of low energy double-ion beam | |||||
| I bundle zirconium ion (Zr+) | II bundle nitrogen ion (N+) | ||||
| The deposition ion energy | 200eV | 200eV | |||
| Ion beam current density | 100μA/cm 2 | 7.5μA/cm 2 | |
| The ion |
2× |
2×2cm 2 | |
| Cycle alternating deposit dosage | 6.25×10 14dose | 25.00×10 14dose | |
| Total cycle count (dosage) | 50(3.125×10 16dose Zr ++1.25×10 17dose N +) | ||
| Growth temperature | 300℃ | ||
| Growth room's vacuum | ≤5×10 -6Pa | ||
| Low energy zirconium ion (Zr+) bundle preparation growing metal zirconium film sample experiment parameter | |||
| Ion energy | 200eV | ||
| Ion beam current density | 7.5μA/cm 2 | ||
| The ion |
2×2cm 2 | ||
| Deposit dose | 3.125×10 17dose | ||
| Growth temperature | 300℃ | ||
| Growth room's vacuum | ≤5×10 -6Pa | ||
| The Measurement results of the metal zirconium film sample that silicon Si Grown obtains | |||
| Color sample | Silver gray | ||
| The crystalline quality test analysis | The X-ray diffraction of metal zirconium film sample (XRD) test result (seeing Fig. 2) shows, realized the single-orientated high crystalline quality growth of metal zirconium film at silicon Si (111) substrate, outside silica removal Si (111) diffraction maximum, only has (002) and (004) diffraction maximum of zirconium Zr in the XRD spectrum. | ||
| The surface topography test analysis | Atomic force surface topography (AFM) test result (seeing Fig. 3) of the metal zirconium film sample on silicon Si (111) substrate, 5 * 5 μ m2R.m.s. roughness (RMS) in the yardstick is 1.40nm, shows that film sample has the smoother flat surface. | ||
| The chemical state test analysis | The x-ray photoelectron power spectrum (XPS) of the metal zirconium film sample on silicon Si (111) substrate, test result shows that sample has the chemical constitution state of metal zirconium, and the Ols peak in the full spectrum is adsorb oxygen impurity and partial oxidation that the sample surface exists, and the Cls peak is the carbon impurity of sample adsorption. |
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: 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 force surface topography (AFM) figure of the metal zirconium film sample that (IBE) growth apparatus prepares outside the ion beam: sample is at 5 * 5 μ m2R.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 constitution 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 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, take the not high low-cost zirconium chloride of purity requirement as raw material, on the clean silicon substrate of crossing with the isotopically pure low energy ion beam bombardment sputter clean of Dan Shu, prepare the thin zirconium nitride of one deck as the barrier layer and the cushion that stop silicon and zirconium ion generation interfacial reaction with the isotopically pure low energy metal zirconium ion beam that produces and nitrogen ion beam first, use again the isotopically pure low energy metal zirconium ion epitaxial growth metal zirconium film of Dan Shu, energy, deposit dose, beam current density, bundle shape of spot and growth temperature by accurate control zirconium ion bundle, in the ultrahigh vacuum growth room, realize low-cost high-purity, high crystalline quality growth and the low-temperature epitaxy of difficult purification, refractory metal zirconium film.
2. the method for preparing thin film material of metal zirconium according to claim 1, refer to especially a kind of ion beam epitaxy growth apparatus and relevant device of utilizing, on substrate, prepare the method for difficult purification, dystectic thin film material of metal zirconium, it is characterized in that, comprise the steps:
Step 1: select the not high low-cost zirconium chloride pressed powder of purity requirement as the raw material of 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 argon gas to produce the raw 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 nitrogen to produce the raw material that are used for growing with the symphysis of zirconium ion fasciculation the nitrogen ion beam of thin zirconium nitride cushion as the Bai Nasi type gas ion source 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 gun 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 induction conduit that container and the Bai Nasi type gas ion source device 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, in ion gun, lead to argon gas, and utilize this ion beam to produce the high-energy argon ion bundle of isotopically pure;
Step 9: open the ultrahigh vacuum 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 isotopically pure is advanced in the retarding lens device in the ultrahigh vacuum growth room, isotopically 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 gas ion source device external admission conduit needle-valve and argon gas;
Step 11: the container of splendid attire nitrogen is connected with the Bai Nasi type gas ion source device external admission conduit of ion beam epitaxy growth apparatus II bundle, by the noticeable degree charge flow rate on it, in ion gun, lead to nitrogen, utilize this ion beam to produce the high energy nitrogen ion beam of isotopically pure;
Step 12: the temperature after the Bai Nasi type solid ion source apparatus baking that continues slow rising I bundle is degassed, make its slow evaporation go out zirconium chloride atmosphere, by the operating temperature in the control ion gun, it is stable to keep its operating air pressure, and utilizes this ion beam to produce the high energy zirconium ion bundle of isotopically 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 gun line regulation device, the high energy zirconium ion bundle of isotopically pure and nitrogen ion beam vertical incidence are alternately advanced in the retarding lens device in the ultrahigh vacuum growth room, the isotopically pure low energy zirconium ion bundle and the nitrogen ion beam that slow down and obtain, dosage and the proportioning of the cycle alternating deposit of setting according to the ion beam flow measuring apparatus, in the thin zirconium nitride layer of substrate preparation growth one deck as stopping the barrier layer of backing material and zirconium ion generation interfacial reaction and the cushion of growing metal zirconium film;
Step 14: close the nitrogen ion beam of ion beam epitaxy growth apparatus II bundle, stop the epitaxial growth of thin zirconium nitride cushion, close air inlet needle-valve and the nitrogen of the Bai Nasi type gas ion source of II bundle;
Step 15: the isotopically pure zirconium ion bundle that produces with ion beam epitaxy growth apparatus I bundle separately, in the ultrahigh vacuum growth room, with lower energy, epitaxial growth thin film material of metal zirconium on thin zirconium nitride cushion.
3. the method for preparing thin film material of metal zirconium according to claim 2 is characterized in that, vacuum≤10 in the ion gun before the baking in the described step 6 is degassed-4Pa, the temperature of Baking out is controlled in the Bai Nasi type solid ion source of I bundle by adjusting its filament heating electric current, crucible heating electric current and arc chamber heating current, the temperature of this ion gun Baking out is 120～140 ℃, the Bai Nasi type gas ion source of II bundle is controlled the temperature of Baking out by adjusting its filament heating electric current, the Baking out temperature is 〉=120 ℃.
4. the method for preparing thin film material of metal zirconium according to claim 2 is characterized in that, the baking of substrate in the described step 7 degas the indoor vacuum of front growth should reach≤5 * 10-6Pa by the heating-up 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 range of the described isotopically 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/cm2, bundle spot size covers whole substrate, energy, beam current density and the scavenging period of the low energy ion beam of determining to clean 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, low energy zirconium ion bundle and the nitrogen ion beam of the described isotopically pure that obtains after slowing down in carry out step 13, by the electric field of readjusting I the electric quadrupole lens devices of restrainting and the electric guider of assisting, magnetic quadrupole lens device and the magnetic field of the magnetic steering device of assisting and the electric field of electrostatic deflection electrodes device of II bundle, so that alternating deposit covers whole substrate to the two bundle spots of restrainting the low energy ion beam of isotopically pures on the substrate, and big or small same position overlaps.
7. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, energy range behind described the slowing down for the preparation of the isotopically pure zirconium ion bundle of the thin zirconium nitride cushion of growth and nitrogen ion beam in carry out step 13 is 15 to 1KeV, according to substrate type difference and the growth needs that growth is adopted, determine energy, beam current density and 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≤5.0 * 10 in the ultrahigh vacuum growth room-6Pa, the preparation growth temperature of thin zirconium nitride cushion is provided by lining heat, and the intensification scope is room temperature to 800 ℃, and the substrate type that adopts 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 growth course, the scanning that swings of low-angle by substrate further improves the epitaxially grown uniformity of thin zirconium nitride cushion.
10. the method for preparing thin film material of metal zirconium according to claim 2, it is characterized in that, the described energy range for the preparation of the isotopically pure low energy zirconium ion of growing metal zirconium film in carry out step 15 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≤5 * 10 in the ultrahigh vacuum growth room-6Pa, the growth temperature of preparation growing metal zirconium film is provided by lining heat, and the intensification scope is room temperature to 800 ℃, and the substrate type that adopts 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, described metal zirconium thin film technology growth in carry out step 15, the scanning that can swing by the low-angle of substrate further improves the uniformity 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, area and the thickness of the metal zirconium film that growth obtains is controlled in described metal zirconium thin film technology growth in carry out step 15, bundle spot size that can be by adjusting epitaxially grown low energy metal zirconium ion beam and the dosage of deposition.
14, the method for preparing thin film material of metal zirconium according to claim 1 and 2 is characterized in that, in vacuum≤5 * 10-6In the ultrahigh vacuum growth room of Pa, adopt silicon as substrate, after substrate cleans through the isotopically pure low energy ion beam bundle bombardment sputter dry method of 300eV, underlayer temperature with 295 ℃～305 ℃, first with the 200eV isotopically pure low energy metal zirconium ion beam and the nitrogen ion beam that produce, alternating deposit prepares the thin zirconium nitride of one deck as the barrier layer and the cushion that stop silicon substrate and zirconium ion generation interfacial reaction, use again the 200eV isotopically pure low energy metal zirconium ion epitaxial growth of Dan Shu, 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/cm2, 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 isotopically pure low energy zirconium ion bundle of thin zirconium nitride cushion preparation and nitrogen ion beam is 6.25 * 1014Dose and 25.00 * 1014Dose, total cycle count is 50, zirconium ion is 1 to 4 with the deposit dose ratio of nitrogen ion.
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| CN113710833A (en) * | 2019-04-22 | 2021-11-26 | 杜鹏 | Molecular beam epitaxy system for directly evaporating pump to cold plate |
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| JP3374842B2 (en) * | 2000-11-10 | 2003-02-10 | 日新電機株式会社 | Method for generating indium ion beam and related devices |
| CN1308145A (en) * | 2000-11-17 | 2001-08-15 | 武汉大学 | Gallium nitride film preparing technology and special equipment |
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| CN113710833A (en) * | 2019-04-22 | 2021-11-26 | 杜鹏 | Molecular beam epitaxy system for directly evaporating pump to cold plate |
| CN113710833B (en) * | 2019-04-22 | 2023-04-28 | 杜鹏 | Molecular beam epitaxy system with direct evaporation pump to cold plate |
| CN112831766A (en) * | 2021-01-04 | 2021-05-25 | 南京佑天金属科技有限公司 | Method for preparing zirconium metal film on silicon substrate by utilizing magnetron sputtering and application |
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