CN114438472A - Large-size ultra-pure vanadium sputtering target material for integrated circuit chip and preparation process thereof - Google Patents
Large-size ultra-pure vanadium sputtering target material for integrated circuit chip and preparation process thereof Download PDFInfo
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- CN114438472A CN114438472A CN202210072450.6A CN202210072450A CN114438472A CN 114438472 A CN114438472 A CN 114438472A CN 202210072450 A CN202210072450 A CN 202210072450A CN 114438472 A CN114438472 A CN 114438472A
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 301
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 287
- 238000005477 sputtering target Methods 0.000 title claims abstract description 80
- 239000013077 target material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 94
- 239000002184 metal Substances 0.000 claims abstract description 94
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- 239000011737 fluorine Substances 0.000 claims abstract description 43
- 238000000151 deposition Methods 0.000 claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 27
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000004544 sputter deposition Methods 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000003870 refractory metal Substances 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010574 gas phase reaction Methods 0.000 abstract description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 59
- 235000013024 sodium fluoride Nutrition 0.000 description 26
- 239000011775 sodium fluoride Substances 0.000 description 26
- 239000012535 impurity Substances 0.000 description 23
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- 238000007740 vapor deposition Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 238000000746 purification Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 229910015255 MoF6 Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- FASQHUUAEIASQS-UHFFFAOYSA-K molybdenum trifluoride Chemical compound F[Mo](F)F FASQHUUAEIASQS-UHFFFAOYSA-K 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000003754 machining Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- 229910015278 MoF3 Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000012536 packaging technology Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910015253 MoF5 Inorganic materials 0.000 description 1
- 229910019787 NbF5 Inorganic materials 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010313 vacuum arc remelting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to the technical field of refractory metal vanadium sputtering targets, and particularly relates to a large-size ultrahigh-purity vanadium sputtering target for an integrated circuit chip and a preparation process thereof, wherein the preparation process comprises the following steps: step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride; step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride; step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method; step S4, depositing ultra-high-purity metal vanadium on a base material, and producing a large-size ultra-high-purity vanadium sputtering target material by a one-step method; the ultra-high-purity vanadium sputtering target material prepared by the invention takes fluorine gas diluted by high-purity nitrogen, high-purity vanadium powder and hydrogen reduction gas as raw materials, and is completed in one step in a special Chemical Vapor Deposition (CVD) device, the reaction process is a continuous gas phase reaction, the product isotropy and batch-to-batch consistency are far superior to those of the traditional vanadium target material, and the purity of the prepared vanadium target material reaches 99.9999%.
Description
Technical Field
The invention belongs to the technical field of refractory metal vanadium sputtering targets, and particularly relates to a large-size ultrahigh-purity vanadium sputtering target for an integrated circuit chip and a preparation process thereof.
Background
Vanadium metal targets are widely used in the electronic and semiconductor fields, such as integrated circuits, semiconductor chips, and the like. In the fabrication of integrated circuits, pure gold is generally used as the surface conductive layer, but gold and silicon wafers tend to generate AuSi low-melting-point compounds, which results in weak bonding between gold and silicon interfaces. The barrier layer needs to be made of metal with high melting point and also needs to bear larger current density, and high-purity refractory metal vanadium is not easy to diffuse, so that the requirement can be met. Therefore, the integrated circuit chip is further upgraded, and the high-purity refractory metal vanadium sputtering target material is an important diffusion-proof barrier layer material.
Metal sputtering targets are key coating materials for semiconductor chips, however, chip fabrication has very high requirements on target purity, texture and performance. Specifically, the manufacturing process of the semiconductor chip can be divided into three major links, namely silicon chip manufacturing, wafer manufacturing, chip packaging and the like, wherein in the aspect of advanced chip packaging, requirements for continuously improving packaging density and packaging efficiency are provided for the packaging technology along with the increase of the number of I/O chips; meanwhile, modern electronic products have more and more complex functions, are light, thin, short and small in size, and also have requirements for continuously reducing the size and the weight of a packaging technology, high-purity vanadium metal is a key material of a Under Bump Metallurgy (UBM) packaging technology and a redistribution layer (RDL) packaging technology, and the preparation technology of the high-purity vanadium target material is very important for achieving the requirements of advanced packaging.
The metal vanadium is used as a refractory metal with higher hardness, so that the processing and forming of the metal vanadium are difficult, and the metal vanadium target material manufactured in the industry at present is mainly prepared into an ideal shape by a vacuum melting method, wherein the vacuum melting is carried out by using high-purity metal vanadium as a raw material, repeatedly melting and purifying, and finally machining, grinding and polishing. The method has the advantages of complex process, inevitable introduction of impurities in the smelting process, difficulty in producing products with larger sizes, low production efficiency, time and labor waste, limitation on product purity, and great difference between the purity of the sputtering target produced by the method and the requirement of the target for electronic-grade products.
For example, CN104894388A discloses a method for preparing a vanadium target by electron beam melting, which uses argon arc welding to connect irregular metal vanadium leftover materials, or uses a vanadium-aluminum alloy containing 90% of vanadium to be placed in a bin of an electromagnetic focusing electron beam melting furnace as a melt electrode, bombards, melts and melts the melt electrode by a high-energy electron beam, and obtains a high-purity vanadium target by evaporation under the condition of continuous vacuum pumping. Although the preparation method can prepare the vanadium target material with the purity of more than 99.95 percent and the density of 6.11 g/cm, meets the requirements of ion plating on the target material, and can also recycle and remelt the waste vanadium target, the preparation method has smaller product size, the purity far cannot reach the use of electronic-grade products, has higher requirements on equipment, and is not suitable for large-scale popularization and use.
CN107385399A discloses an extrusion method of a vanadium tube target, which comprises the steps of smelting a metal vanadium block by a vacuum electron beam to obtain a high-purity vanadium ingot with the diameter of phi 150-phi 215mm, and polishing the outer surface of the vanadium ingot; then, digging out a vanadium rod with the diameter of phi 50-phi 125mm by means of electric spark punching and linear cutting; coating the inner wall, the outer wall and the end faces of the vanadium tube blank by using a sheath material, and welding and sealing; heating to 750-1000 ℃, preserving heat for 1-2 hours, then extruding the vanadium tube blank with the sheath to obtain a vanadium tube with an intermediate size, and finally obtaining the required finished product vanadium tube target through straightening treatment and machining. The density of the finished vanadium tube target is lower, and the extrusion method of the vanadium tube target is greatly different from the preparation method of the planar target.
CN112779508A discloses a preparation method of a high-purity vanadium target blank and a method for preparing a high-purity vanadium target material by using the same, wherein a vanadium ingot is prepared by smelting in any one mode of electron beam, vacuum arc remelting or vacuum induction smelting and then pouring. And cutting the vanadium cast ingot according to the target size, strictly limiting the temperature of the secondary annealing to be 450-550 ℃ by utilizing the synergistic coupling effect of forging, annealing, rolling and secondary annealing, keeping the heat preservation time of the annealing to be 60-120min, and then cooling by water to obtain the high-purity vanadium target blank. The high-purity vanadium target material has small size, the purity can not meet the use requirement of electronic-grade products, the smelting needs to be repeatedly operated, the time and labor are wasted, the efficiency is low, and the high-purity vanadium target material is difficult to be used for industrial production.
The purity of materials used in integrated circuits is generally required to reach 4N5, and with the rapid increase of the number of integrated devices per unit area, the influence of the purity factor of thin film materials is increasing, and the purity factor of thin film materials is required to reach more than 6N in advanced electronic industry.
In summary, there is a need to develop an effective method for preparing a high-purity large-size vanadium target for an integrated circuit chip, so as to prepare a vanadium target with high purity (99.9999%) and large size (greater than 500mm), so as to meet the requirements of the electronic industry such as the integrated circuit chip.
Disclosure of Invention
The invention provides a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip and a preparation process thereof.
In order to solve the technical problems, the invention provides a preparation process of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip, which comprises the following steps: step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride; step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride; step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method; and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In another aspect, the invention further provides a large-size ultrahigh-purity vanadium sputtering target for an integrated circuit chip, which is obtained by the preparation process.
The invention has the beneficial effects that the large-size ultra-high-purity vanadium sputtering target material for the integrated circuit chip and the preparation process thereof have the following characteristics:
1. the ultrahigh-purity vanadium sputtering target material prepared by the invention takes high-purity fluorine gas (diluted by nitrogen), high-purity vanadium powder and reducing gas (hydrogen) as raw materials, and is finished in one step in chemical vapor deposition equipment, the reaction process is a continuous gas-phase reaction, and the product consistency in each direction and batch are far superior to that of the traditional vanadium target material;
2. the purity of the ultra-high purity vanadium sputtering target material manufactured by the invention can reach more than 99.9999 percent, and the material purity is far superior to that of the vanadium sputtering target material produced by the current vacuum melting process;
3. the relative density of the high-purity vanadium sputtering target material prepared by the invention is not lower than 99.5 percent;
4. the method for manufacturing the ultra-pure vanadium sputtering target can be used for producing a large-size vanadium target with the diameter of more than 500mm, the thickness of the vanadium target can be controlled by deposition time, and the maximum thickness can be stably controlled to be 1-40 mm;
5. the average crystal grain on the sputtering surface of the ultra-high purity vanadium sputtering target material manufactured by the invention can control the size of the crystal grain within the range of 20-50 mu m according to the use requirement;
6. the ultra-pure vanadium sputtering target or the vanadium target blank manufactured by the invention can be deposited on copper, aluminum, nickel, titanium or other base materials, and a Cu/W composite transition layer is deposited on a base body with corrosion pollution;
7. the deposition direction or the grain growth direction of the ultra-pure vanadium sputtering target material prepared by the invention is vertical to the sputtering surface, and grains are uniformly distributed in the vertical direction of the sputtering surface, so that the film forming quality is completely consistent during sputtering;
8. the high-purity large-size vanadium target product produced by the method has the advantages of simple process, large product size, high purity, high density, low cost, good consistency and the like, and is very suitable for high-end large-size integrated circuits and semiconductor chips.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram of a large-size ultra-high purity vanadium sputtering target for integrated circuit chips according to the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, the invention provides a preparation process of a large-size ultra-high purity vanadium sputtering target for an integrated circuit chip, which comprises the following steps: step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride; step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride; step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method; and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In this embodiment, specifically, the fluorine gas is diluted with nitrogen gas.
In this embodiment, optionally, in the step S1, the temperature of the reaction between vanadium and fluorine gas under the high temperature condition is 300 ℃; and introducing the crude vanadium pentafluoride into a low-temperature container to be collected in a liquid form.
Specifically, by chemical reaction (2V + 5F)3→2VF5) Fully reacting high-purity metal vanadium powder with high-purity fluorine gas (diluted by nitrogen), wherein the reaction temperature is higher than 300 DEG CUnder the condition of temperature, the fluorinated product passes through a 1-3-stage receiver, and high-boiling-point impurities (N) are recovered at the 1 st stage2、CO、NF3、CF4、NbF5、CO2And the like), recovering vanadium pentafluoride in the 2 nd stage, recovering excessive fluorine and low-boiling-point impurities in the 3 rd stage, and introducing the vanadium pentafluoride prepared by the reaction into another low-temperature container to be collected in a liquid form.
In this embodiment, optionally, the content of vanadium in the vanadium sputtering target is 99.999% -99.99999%.
In this embodiment, optionally, the relative density of the vanadium sputtering target is not lower than 99.5%, so that the fluorine gas and the vanadium react more sufficiently, and the efficiency is higher, so as to obtain ultra-high-purity vanadium pentafluoride.
Optionally, the crude vanadium pentafluoride can be purified repeatedly by a vacuum distillation method, an adsorption method and a metal reduction method until the purity of the high-purity vanadium pentafluoride reaches 99.9999%.
Specifically, the obtained crude vanadium pentafluoride is purified by a vacuum distillation method to further remove volatile components with a boiling point greatly different from that of the vanadium pentafluoride; compared with the traditional condensation method, the vacuum distillation reduces the boiling point by reducing the pressure in the system, effectively avoids the decomposition and reaction of impurities due to overhigh temperature, has higher efficiency, and can carry out deeper purification at lower temperature. Sodium fluoride (NaF) or potassium fluoride (KF) is used as adsorbent, and one of them is filled into an adsorption container, VF5The gas passes through an adsorption vessel filled with NaF or KF, and HF reacts with the NaF (or KF) at a proper adsorption temperature to generate a non-volatile substance NaHF2Or KHF2To remove HF; metal impurities and high-melting point fluoride can be removed by replacing the conversion container; due to MoF6Melting Point (17.4 ℃ C.) and VF5The melting point (19.5 ℃) is close, and the distillation removal is difficult, so that the metal reduction is adopted to remove MoF5Using MoF6The property of easy reduction of metal is in a temperature range suitable for reaction, one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like is added into a columnar reactor, and the temperature is controlled to be between 100 and 500 DEG CWhich reduces MoF6Is molybdenum trifluoride (MoF)3High melting point and can be stably accumulated on the metal surfaces). And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Optionally, the ultrahigh-purity metal vanadium is deposited on the vanadium target blank on the non-back plate material by chemical vapor deposition equipment, and the vanadium target blank is bound with the back plate after machining, high-temperature heat treatment and surface treatment, and then the ultrahigh-purity large-size vanadium target product is manufactured by subsequent processes.
Optionally, when the high-purity vanadium pentafluoride is reduced into the ultra-high-purity vanadium metal by using a reducing gas such as hydrogen, the reaction temperature is controlled to be 900-1000 ℃, and N is applied before the reaction2And fully purging the equipment pipeline and the cavity.
In this embodiment, the base material may optionally include copper, aluminum, nickel, and titanium.
Specifically, the vanadium metal is deposited on copper, aluminum, nickel, titanium or other base materials, when the vanadium metal is deposited on the base materials which are easy to react with reaction gases (hydrogen and hydrogen fluoride) or easily fall off due to overlarge stress, a transition layer is adopted, a Cu/W composite transition layer is deposited on the base materials, and then the vanadium metal is deposited, wherein the transition layer is as thin as possible, so that the base materials are prevented from being corroded, polluted and falling off.
Optionally, when the vanadium sputtering target is strip-shaped, the length of the vanadium sputtering target is 100-1000 mm, and the width of the vanadium sputtering target is 100-600 mm.
Optionally, when the vanadium sputtering target is cylindrical, the diameter of the vanadium sputtering target is 100-600 mm, and the thickness of the vanadium sputtering target is 1-40 mm.
Optionally, the deposition direction of the metal vanadium or the growth direction of the crystal grains in the vanadium sputtering target material is perpendicular to the sputtering surface, and the size and orientation of the crystal grains tend to be consistent.
Optionally, the average grain size of the vanadium sputtering target is 20-50 μm.
Specifically, by controlling the deposition speed of the vanadium target and controlling the grain size and the crystal face orientation, the target is uniform in structural components and consistent in grain orientation, the problem of preferential sputtering is avoided, the stability in the sputtering process is ensured, the consistency of surface components of the target after use is ensured, the deposition direction is perpendicular to the basal plane during deposition so as to ensure that the crystal face orientation can be perpendicular to the sputtering direction, when the deposition temperature is less than 900 ℃, the deposition layer is mainly a layered structure, the deposition layer does not become thick along with the temperature rise, and when the temperature is more than 800 ℃, a local columnar crystal structure begins to appear; when the temperature is 900 ℃, the deposition structure mainly consists of slender columnar crystals vertical to the deposition surface, the temperature is further raised, and the crystal grains grow gradually; when the temperature is more than 1000 ℃, the columnar crystal structure of the deposited layer becomes relatively coarse.
Further, the invention also provides a large-size ultrahigh-purity vanadium sputtering target material for the integrated circuit chip, which is obtained by adopting the preparation process.
Example 1
A preparation method of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip comprises the following steps:
step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In step S1, the fluorine gas (diluted with nitrogen gas) is a high-purity fluorine gas (diluted with nitrogen gas) of 99.999% or more, and the metal vanadium is a high-purity vanadium powder of 99.95% or more.
Specifically, in the step S1, vanadium and fluorine gas (diluted with nitrogen gas) are sufficiently reacted, the reaction is performed at a high temperature of more than 300 ℃, the fluorination product passes through a 1-3-stage receiver, high-boiling-point impurities are recovered in the 1 st stage, vanadium pentafluoride is recovered in the 2 nd stage, excess fluorine and low-boiling-point impurities are recovered in the 3 rd stage, and vanadium pentafluoride obtained by the reaction is introduced into another low-temperature container and collected in a liquid form.
More specifically, the process comprisesPurifying the crude vanadium pentafluoride obtained in the step S1 by a vacuum distillation method to further remove volatile components with a boiling point greatly different from that of the vanadium pentafluoride; sodium fluoride (NaF) is used as adsorbent, and one of the NaF and the NaF is filled into an adsorption container, VF5The gas passes through an adsorption container filled with NaF, HF reacts with NaF at a proper adsorption temperature to generate NaHF serving as a nonvolatile substance2To remove HF; metal impurities and high-melting point fluoride can be removed by replacing the conversion container; MoF removal by metal reduction6Adding one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like into a columnar reactor within a temperature range suitable for reaction to reduce MoF6Is MoF3. And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Specifically, the reducing gas H is used by the chemical vapor deposition apparatus via step S32Reducing the high-purity vanadium pentafluoride prepared in S2 into ultra-high-purity metal vanadium at the reaction temperature of 900 ℃, and applying N before the reaction2And fully purging the equipment pipeline and the cavity.
Specifically, the ultra-pure metal vanadium obtained in the step S3 is deposited on the vanadium target blank on the non-backplate material by the chemical vapor deposition equipment, and the vanadium target blank is bound with the backplate after cutting, high-temperature heat treatment and surface treatment, and then the vanadium target is manufactured into the product vanadium target after the subsequent processes. Wherein the subsequent processes comprise precision machining, cleaning and the like.
Specifically, the vanadium content in the high-purity vanadium target blank obtained in step S4 is 99.9999%. Furthermore, by utilizing the principles of vacuum distillation purification of vanadium pentafluoride and directional growth purification of vapor deposition crystal, the ultra-high purity metal vanadium target product can be produced, and the purity of the material is 99.9999% through detection.
Specifically, the measured relative density of the ultra-high purity vanadium target material blank obtained in the step S4 is 99.7%.
Specifically, the ultra-high purity vanadium target blank obtained in the step S4 is a strip blank with a length of 800mm and a width of 300mm, and further, a vanadium target blank product with a thickness of 30mm is produced by deposition by using a continuous vapor deposition grain growth principle.
Specifically, through metallographic observation, the deposition direction or the grain growth direction of the ultra-high purity metal vanadium in the ultra-high purity vanadium target blank obtained in step S4 is perpendicular to the sputtering surface, the grain size and orientation in the direction perpendicular to the sputtering surface tend to be consistent, and the average grain size on the sputtering surface is 22 um.
More specifically, vanadium targets or vanadium target blanks with different sizes or different shapes can be deposited by adjusting the material, the shape and the size of the deposition substrate; if high-purity vanadium is directly deposited on a copper or copper alloy base material meeting the use requirement of the target, the high-purity large-size vanadium target meeting the use requirement can be produced in one step. Furthermore, the vapor deposition reaction is a continuous gaseous reaction, the reaction process is uniform, and the product consistency is good; the vanadium target material is prepared by adopting a one-step method, secondary processing pollution is avoided, the quality of the vanadium target material product is favorably ensured, and the production cost is low.
Example 2
A preparation method of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip comprises the following steps:
step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In step S1, the fluorine gas (diluted with nitrogen gas) is a high-purity fluorine gas (diluted with nitrogen gas) of 99.999% or more, and the metal vanadium is a high-purity vanadium powder of 99.95% or more.
Specifically, in the step S1, vanadium and fluorine gas (diluted with nitrogen gas) are sufficiently reacted, the reaction is performed at a high temperature of more than 300 ℃, the fluorination product passes through a 1-3-stage receiver, high-boiling-point impurities are recovered in the 1 st stage, vanadium pentafluoride is recovered in the 2 nd stage, excess fluorine and low-boiling-point impurities are recovered in the 3 rd stage, and vanadium pentafluoride obtained by the reaction is introduced into another low-temperature container and collected in a liquid form.
More specifically, the crude vanadium pentafluoride obtained in step S1 is purified by a vacuum distillation method to further remove volatile components having a boiling point that is greatly different from that of vanadium pentafluoride; sodium fluoride (NaF) is used as adsorbent, and one of the NaF and the NaF is filled into an adsorption container, VF5The gas passes through an adsorption container filled with NaF, HF reacts with NaF at a proper adsorption temperature to generate NaHF serving as a nonvolatile substance2To remove HF; metal impurities and high-melting point fluoride can be removed by replacing the conversion container; MoF removal by metal reduction6Adding one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like into a columnar reactor within a temperature range suitable for reaction to reduce MoF6Is MoF3. And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Specifically, the reducing gas H is used by the chemical vapor deposition apparatus via step S32Reducing the high-purity vanadium pentafluoride prepared in S2 into ultra-high-purity vanadium metal at the reaction temperature of 920 ℃, and applying N before the reaction2And fully purging the equipment pipeline and the cavity.
Specifically, the ultra-pure metal vanadium obtained in the step S3 is deposited on the vanadium target blank on the non-backplate material by the chemical vapor deposition equipment, and the vanadium target blank is bound with the backplate after cutting, high-temperature heat treatment and surface treatment, and then the vanadium target is manufactured into the product vanadium target after the subsequent processes. Wherein the subsequent processes comprise precision machining, cleaning and the like.
Specifically, the content of vanadium in the ultra-high purity vanadium target blank obtained in step S3 is 99.9999%. Furthermore, by utilizing the principles of vacuum distillation purification of vanadium pentafluoride and directional growth purification of vapor deposition crystal, the ultra-high purity metal vanadium target product can be produced, and the purity of the material is 99.9999% through detection.
Specifically, the measured relative density of the ultra-high purity vanadium target material blank obtained in the step S4 is 99.6%.
Specifically, the ultra-high purity vanadium target billet obtained in the step S4 is a cylindrical billet with a diameter of 500mm and a thickness of 30 mm.
Specifically, through metallographic observation, the deposition direction or the grain growth direction of the ultra-high purity metal vanadium in the ultra-high purity vanadium target blank obtained in step S4 is perpendicular to the sputtering surface, the grain size and orientation in the direction perpendicular to the sputtering surface tend to be consistent, and the average grain size on the sputtering surface is 25 um.
More specifically, vanadium targets or vanadium target blanks with different sizes or different shapes can be deposited by adjusting the material, the shape and the size of the deposition substrate; if high-purity vanadium is directly deposited on a copper or copper alloy base material meeting the use requirement of the target, the high-purity large-size vanadium target meeting the use requirement can be produced in one step. Furthermore, the vapor deposition reaction is a continuous gaseous reaction, the reaction process is uniform, and the product consistency is good; the vanadium target material is prepared by adopting a one-step method, secondary processing pollution is avoided, the quality of the vanadium target material product is favorably ensured, and the production cost is low.
Example 3
A preparation method of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip comprises the following steps:
step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In step S1, the fluorine gas (diluted with nitrogen gas) is a high-purity fluorine gas (diluted with nitrogen gas) of 99.999% or more, and the metal vanadium is a high-purity vanadium powder of 99.95% or more.
Specifically, the vanadium and the fluorine gas (diluted by nitrogen) in the step S1 are fully reacted, the reaction needs to pass through a 1-3-stage receiver under the high temperature condition of more than 300 ℃, the high boiling point impurities are recovered at the 1 st stage, the vanadium pentafluoride is recovered at the 2 nd stage, the excessive fluorine and the low boiling point impurities are recovered at the 3 rd stage, and the vanadium pentafluoride prepared by the reaction is introduced into another low-temperature container to be collected in a liquid form.
More specifically, the crude vanadium pentafluoride obtained in step S1 is purified by a vacuum distillation method to further remove volatile components having a boiling point that is greatly different from that of vanadium pentafluoride; sodium fluoride (NaF) is used as adsorbent, and one of the NaF and the NaF is filled into an adsorption container, VF5The gas passes through an adsorption container filled with NaF, HF reacts with NaF at a proper adsorption temperature to generate NaHF serving as a nonvolatile substance2To remove HF; metal impurities and high-melting point fluoride can be removed by replacing the conversion container; MoF removal by metal reduction6Adding one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like into a columnar reactor within a temperature range suitable for reaction to reduce MoF6Is MoF3. And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Specifically, the reducing gas H is used by the chemical vapor deposition apparatus via step S32Reducing the high-purity vanadium pentafluoride prepared in S2 into ultra-high-purity vanadium metal, wherein the reaction temperature is about 950 ℃, and N is applied before the reaction2And fully purging the equipment pipeline and the cavity.
Specifically, the ultra-high purity vanadium obtained in step S3 is deposited on the vanadium target on the copper back plate material by chemical vapor deposition equipment, and the vanadium target is manufactured into a finished vanadium target after heat treatment and precision machining.
Specifically, the content of vanadium in the ultra-high purity vanadium target obtained in step S4 is 99.9999%. Furthermore, by utilizing the principles of vacuum distillation purification of vanadium pentafluoride and directional growth purification of vapor deposition crystal, the ultra-high purity metal vanadium target product can be produced, and the purity of the material is 99.9999% through detection.
Specifically, the ultra-high purity vanadium target obtained in step S4 has a measured relative density of 99.5%.
Specifically, the ultra-high purity vanadium target obtained in the step S4 has a strip shape with a length of 800mm and a width of 300 mm. Further, by utilizing the principle of continuous vapor deposition grain growth, a vanadium target product with the thickness of 30mm is produced by deposition.
Specifically, through metallographic observation, the deposition direction or the grain growth direction of the ultra-high purity metal vanadium in the high-purity vanadium target material or vanadium target material blank obtained in the step S4 is perpendicular to the sputtering surface, the grain size and orientation in the direction perpendicular to the sputtering surface tend to be consistent, and the average grain size on the sputtering surface is 32 um.
More specifically, vanadium targets or vanadium target blanks with different sizes or different shapes can be deposited by adjusting the material, the shape and the size of the deposition substrate; if ultra-high purity vanadium is directly deposited on a copper or copper alloy matrix material meeting the use requirement of the target, the high-purity large-size vanadium target meeting the use requirement can be produced in one step. Furthermore, the vapor deposition reaction is a continuous gaseous reaction, the reaction process is uniform, and the product consistency is good; the vanadium target material is prepared by adopting a one-step method, secondary processing pollution is avoided, the quality of the vanadium target material product is favorably ensured, and the production cost is low.
Example 4
A preparation method of a large-size ultra-pure vanadium sputtering target material for an integrated circuit chip comprises the following steps:
step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In step S1, the fluorine gas (diluted with nitrogen gas) is a high-purity fluorine gas (diluted with nitrogen gas) of 99.999% or more, and the metal vanadium is a high-purity vanadium powder of 99.95% or more.
Specifically, in the step S1, vanadium and fluorine gas (diluted with nitrogen gas) are sufficiently reacted, the reaction is performed at a high temperature of more than 300 ℃, the fluorination product passes through a 1-3-stage receiver, high-boiling-point impurities are recovered in the 1 st stage, vanadium pentafluoride is recovered in the 2 nd stage, excess fluorine and low-boiling-point impurities are recovered in the 3 rd stage, and vanadium pentafluoride obtained by the reaction is introduced into another low-temperature container and collected in a liquid form.
More specifically, the crude vanadium pentafluoride obtained in step S1 is purified by a vacuum distillation method to further remove volatile components having a boiling point that is greatly different from that of vanadium pentafluoride; sodium fluoride (NaF) is used as adsorbent, and one of the NaF and the NaF is filled into an adsorption container, VF5The gas passes through an adsorption container filled with NaF, HF reacts with NaF at a proper adsorption temperature to generate NaHF serving as a nonvolatile substance2To remove HF; metal impurities and high-melting point fluoride can be removed by replacing the conversion container; MoF removal by metal reduction6Adding one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like into a columnar reactor within a temperature range suitable for reaction to reduce MoF6Is MoF3. And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Specifically, the reducing gas H is used by the chemical vapor deposition apparatus via step S32Reducing the high-purity vanadium pentafluoride prepared in S2 into ultra-high-purity metal vanadium, controlling the reaction temperature at 950 ℃, and applying N before the reaction2And fully purging the equipment pipeline and the cavity.
Specifically, the ultra-high purity vanadium obtained in step S3 is deposited on the vanadium target on the copper back plate material by chemical vapor deposition equipment, and the vanadium target is manufactured into a finished vanadium target after heat treatment and precision machining.
Specifically, the vanadium content in the high-purity vanadium target obtained in the step S4 is 99.9999%. Furthermore, by utilizing the principles of vacuum distillation purification of vanadium pentafluoride and directional growth purification of vapor deposition crystal, the ultra-high purity metal vanadium target product can be produced, and the purity of the material is 99.9999% through detection.
Specifically, the measured relative density of the ultra-high purity vanadium target material blank obtained in the step S4 is 99.5%.
Specifically, the ultra-high purity vanadium target product obtained in the step S4 is a cylindrical vanadium target product with a diameter of 500mm and a thickness of 30 mm.
Specifically, through metallographic observation, the deposition direction or the grain growth direction of the ultra-high purity metal vanadium in the ultra-high purity vanadium target material or vanadium target material blank obtained in step S4 is perpendicular to the sputtering surface, the grain size and orientation in the direction perpendicular to the sputtering surface tend to be consistent, and the average grain size on the sputtering surface is 32 um.
More specifically, vanadium targets or vanadium target blanks with different sizes or different shapes can be deposited by adjusting the material, the shape and the size of the deposition substrate; if high-purity vanadium is directly deposited on a copper or copper alloy base material meeting the use requirement of the target, the high-purity large-size vanadium target meeting the use requirement can be produced in one step. Furthermore, the vapor deposition reaction is a continuous gaseous reaction, the reaction process is uniform, and the product consistency is good; the vanadium target material is prepared by adopting a one-step method, secondary processing pollution is avoided, the quality of the vanadium target material product is favorably ensured, and the production cost is low.
Example 5
A preparation method of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip comprises the following steps:
step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In step S1, the fluorine gas (diluted with nitrogen gas) is a high-purity fluorine gas (diluted with nitrogen gas) of 99.999% or more, and the metal vanadium is a high-purity vanadium powder of 99.95% or more.
Specifically, in the step S1, vanadium and fluorine gas (diluted with nitrogen gas) are sufficiently reacted, the reaction is performed at a high temperature of more than 300 ℃, the fluorination product passes through a 1-3-stage receiver, high-boiling-point impurities are recovered in the 1 st stage, vanadium pentafluoride is recovered in the 2 nd stage, excess fluorine and low-boiling-point impurities are recovered in the 3 rd stage, and vanadium pentafluoride obtained by the reaction is introduced into another low-temperature container and collected in a liquid form.
More specifically, the crude vanadium pentafluoride obtained in step S1 is purified by a vacuum distillation method to further remove volatile components having a boiling point that is greatly different from that of vanadium pentafluoride; sodium fluoride (NaF) is used as adsorbent, and one of the NaF and the NaF is filled into an adsorption container, VF5The gas passes through an adsorption container filled with NaF, HF reacts with NaF at a proper adsorption temperature to generate NaHF serving as a nonvolatile substance2To remove HF; the metal impurities can be removed by replacing the conversion container; MoF removal by metal reduction6Adding one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like into a columnar reactor within a temperature range suitable for reaction to reduce MoF6Is MoF3. And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Specifically, the reducing gas H is used by the chemical vapor deposition apparatus via step S32Reducing the high-purity vanadium pentafluoride prepared in S2 into ultra-high-purity metal vanadium, controlling the reaction temperature at 920 ℃, and applying N before the reaction2And fully purging the equipment pipeline and the cavity.
Specifically, the high-purity metal vanadium obtained in the step S3 is deposited on the vanadium target deposited with the Cu/W composite transition layer on the titanium substrate material by using a chemical vapor deposition apparatus, and the vanadium target is manufactured into a finished vanadium target after heat treatment and precision processing.
Specifically, the vanadium content in the high-purity vanadium target obtained in the step S4 is 99.9999%. Furthermore, by utilizing the principles of vacuum distillation purification of vanadium pentafluoride and directional growth purification of vapor deposition crystal, the ultra-high purity metal vanadium target product can be produced, and the purity of the material is 99.9999% through detection.
Specifically, the ultra-high purity vanadium target obtained in step S4 has a measured relative density of 99.5%.
Specifically, the ultra-high purity vanadium target obtained in the step S4 has a strip shape with a length of 800mm and a width of 300 mm. Further, by utilizing the principle of continuous vapor deposition grain growth, a vanadium target product with the thickness of 25mm is produced by deposition.
Specifically, through metallographic observation, the deposition direction or the grain growth direction of the ultra-high purity metal vanadium in the ultra-high purity vanadium target obtained in step S4 is perpendicular to the sputtering surface, the grain size and orientation in the direction perpendicular to the sputtering surface tend to be consistent, and the average grain size on the sputtering surface is 25 um.
More specifically, vanadium targets or vanadium target blanks with different sizes or different shapes can be deposited by adjusting the material, the shape and the size of the deposition substrate; if high-purity vanadium is directly deposited on a copper or copper alloy base material meeting the use requirement of the target, the high-purity large-size vanadium target meeting the use requirement can be produced in one step. Furthermore, the vapor deposition reaction is a continuous gaseous reaction, the reaction process is uniform, and the product consistency is good; the vanadium target material is prepared by adopting a one-step method, secondary processing pollution is avoided, the quality of the vanadium target material product is favorably ensured, and the production cost is low.
Example 6
A preparation method of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip comprises the following steps:
step S1, reacting vanadium with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
In step S1, the fluorine gas (diluted with nitrogen gas) is a high-purity fluorine gas (diluted with nitrogen gas) of 99.999% or more, and the metal vanadium powder is a high-purity vanadium powder of 99.96% or more.
Specifically, the high-purity metal vanadium powder in the step S1 is fully reacted with high-purity fluorine gas (diluted by nitrogen gas), the reaction needs to pass through a 1-3-stage receiver under a high-temperature condition of more than 300 ℃, high-boiling-point impurities are recovered in the 1 st stage, vanadium pentafluoride is recovered in the 2 nd stage, excessive fluorine and low-boiling-point impurities are recovered in the 3 rd stage, and the vanadium pentafluoride prepared by the reaction is introduced into another low-temperature container to be collected in a liquid form.
More specifically, the crude vanadium pentafluoride obtained in step S1 is purified by a vacuum distillation method to further remove volatile components having a boiling point that is greatly different from that of vanadium pentafluoride; sodium fluoride (NaF) is used as adsorbent, and one of the NaF and the NaF is filled into an adsorption container, VF5The gas passes through an adsorption container filled with NaF, HF reacts with NaF at a proper adsorption temperature to generate NaHF serving as a nonvolatile substance2To remove HF; the metal impurities can be removed by replacing the conversion container; MoF removal by metal reduction6Adding one of copper, nickel, iron, cobalt, zinc, titanium, calcium and the like into a columnar reactor within a temperature range suitable for reaction to reduce MoF6Is MoF3. And repeating the steps until the purity of the vanadium pentafluoride reaches 99.9999%.
Specifically, the reducing gas H is used by the chemical vapor deposition apparatus via step S32Reducing the high-purity vanadium pentafluoride prepared in S2 into ultra-high-purity metal vanadium, controlling the reaction temperature at 920 ℃, and applying N before the reaction2And fully purging the equipment pipeline and the cavity.
Specifically, the high-purity metal vanadium obtained in the step S3 is deposited on the vanadium target deposited with the Cu/W composite transition layer on the titanium substrate material by using a chemical vapor deposition apparatus, and the vanadium target is manufactured into a finished vanadium target after heat treatment and precision processing.
Specifically, the vanadium content in the high-purity vanadium target obtained in the step S4 is 99.9999%. Furthermore, by utilizing the principles of vacuum distillation purification of vanadium pentafluoride and directional growth purification of vapor deposition crystal, the ultra-high purity metal vanadium target product can be produced, and the purity of the material is 99.9999% through detection.
Specifically, the ultra-high purity vanadium target obtained in step S4 has a measured relative density of 99.6%.
Specifically, the ultra-high purity vanadium target obtained in step S4 is a vanadium target product with a diameter of 500mm and a thickness of 30 mm.
Specifically, through metallographic observation, the deposition direction or the grain growth direction of the ultra-high purity metal vanadium in the ultra-high purity vanadium target obtained in step S4 is perpendicular to the sputtering surface, the grain size and orientation in the direction perpendicular to the sputtering surface tend to be consistent, and the average grain size on the sputtering surface is 25 um.
More specifically, vanadium targets or vanadium target blanks with different sizes or different shapes can be deposited by adjusting the material, the shape and the size of the deposition substrate; if high-purity vanadium is directly deposited on a copper or copper alloy base material meeting the use requirement of the target, the high-purity large-size vanadium target meeting the use requirement can be produced in one step. Furthermore, the vapor deposition reaction is a continuous gaseous reaction, the reaction process is uniform, and the product consistency is good; the vanadium target material is prepared by adopting a one-step method, secondary processing pollution is avoided, the quality of the vanadium target material product is favorably ensured, and the production cost is low.
In summary, compared with the prior art, the preparation method of the large-size vanadium sputtering target for the integrated circuit chip of the invention has the following characteristics: the ultrahigh-purity vanadium sputtering target material prepared by the invention takes high-purity fluorine gas (diluted by nitrogen), high-purity vanadium powder and reducing gas (hydrogen) as raw materials, and is finished in one step in chemical vapor deposition equipment, the reaction process is a continuous gas-phase reaction, and the product consistency in each direction and batch are far superior to that of the traditional vanadium target material; the purity of the ultra-pure vanadium sputtering target material manufactured by the invention can reach more than 99.9999 percent, and the material purity is far superior to that of the vanadium sputtering target material produced by a vacuum melting process; the relative density of the high-purity vanadium sputtering target material prepared by the invention is not lower than 99.5 percent; the method for manufacturing the ultra-pure vanadium sputtering target can be used for producing a large-size vanadium target with the diameter of more than 500mm, the thickness of the vanadium target can be controlled by deposition time, and the maximum thickness can be stably controlled to be 1-40 mm; the average crystal grain on the sputtering surface of the ultra-high purity vanadium sputtering target material manufactured by the invention can control the size of the crystal grain within the range of 20-50 mu m according to the use requirement; the ultra-pure vanadium sputtering target or the vanadium target blank manufactured by the invention can be deposited on copper, aluminum, nickel, titanium or other base materials, and a Cu/W composite transition layer is deposited on a base body which is polluted by corrosion, reacts or is easy to fall off; the deposition direction or the grain growth direction of the ultra-pure vanadium sputtering target material prepared by the invention is vertical to the sputtering surface, and grains are uniformly distributed in the vertical direction of the sputtering surface, so that the film forming quality is completely consistent during sputtering; the high-purity large-size vanadium target product for the integrated circuit chip produced by the invention has the advantages of simple process, large product size, high purity, high density, low cost, good consistency and the like, and is very suitable for high-end large-size integrated circuits and semiconductor chips.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation process of a large-size ultrahigh-purity vanadium sputtering target material for an integrated circuit chip is characterized by comprising the following steps of:
step S1, reacting the vanadium powder with fluorine gas at high temperature to prepare crude vanadium pentafluoride;
step S2, purifying the crude vanadium pentafluoride by a vacuum distillation method, an adsorption method and a metal reduction method to obtain high-purity vanadium pentafluoride;
step S3, reducing the high-purity vanadium pentafluoride into ultra-high-purity vanadium metal by adopting a chemical vapor deposition method;
and step S4, depositing the ultra-high-purity metal vanadium on the base material, and producing the large-size ultra-high-purity vanadium sputtering target material by a one-step method.
2. The process for preparing a sputtering target according to claim 1,
in the step S1, the reaction temperature of the vanadium and the fluorine gas under the high-temperature condition is 300 ℃;
and introducing the crude vanadium pentafluoride into a low-temperature container to be collected in a liquid form.
3. The process for preparing a sputtering target according to claim 1,
the content of vanadium in the vanadium sputtering target material is 99.9999-99.99999%.
4. The process for preparing a sputtering target according to claim 1,
the relative density of the vanadium sputtering target is not less than 99.5%.
5. The process for preparing a sputtering target according to claim 1,
the matrix material includes copper, aluminum, nickel, titanium, and the like.
6. The process for preparing a sputtering target according to claim 1,
when the vanadium sputtering target material is strip-shaped, the length of the vanadium sputtering target material is 100-1000 mm, and the width of the vanadium sputtering target material is 100-600 mm.
7. The process for preparing a sputtering target according to claim 1,
when the vanadium sputtering target material is cylindrical, the diameter of the vanadium sputtering target material is 100-600 mm, and the thickness of the vanadium sputtering target material is 1-40 mm.
8. The process for preparing a sputtering target according to claim 1,
the deposition direction of the metal vanadium or the growth direction of crystal grains in the vanadium sputtering target material is vertical to the sputtering surface.
9. The process for preparing a sputtering target according to claim 1,
the average grain size of the vanadium sputtering target is 20-50 mu m.
10. A large-size ultra-high purity vanadium sputtering target for integrated circuit chips prepared by the preparation method as set forth in claim 1.
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