CN103966566A - Preparing method for double-layer high-entropy alloy diffusion barrier layer - Google Patents
Preparing method for double-layer high-entropy alloy diffusion barrier layer Download PDFInfo
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Abstract
The invention discloses a preparing method for a double-layer high-entropy alloy diffusion barrier layer. The method comprises the following steps: cleaning a single crystal Si base in an ultrasonic way; removing impurities in the single crystal Si base in an anti-sputtering cleaning way, and removing impurities in target materials and target sheets in a pre-sputtering cleaning way; depositing an HEANs thin film on the single crystal Si base in a sputtering way under the condition that the flow ratio of Ar to N is 1:(0.65-0.9); depositing an HEAs thin film on the ANs thin film in a sputtering way by using the Ar as the working gas when the thickness of the HEANs thin film reaches the designed thickness; adjusting the vacuum degree in a furnace to the degree not lower than 10-3 Pa when the thickness of the HEAs thin film reaches the designed thickness, and naturally cooling and releasing from the furnace to obtain the double-layer high-entropy alloy diffusion barrier layer. For the double-layer high-entropy alloy diffusion barrier layer obtained by the method, the method has the advantages that the bonding strength among the base, the Cu and the barrier layer is improved, and the whole heat stability of the diffusion barrier layer is improved. The method also has the characteristics of skillful technique for the preparing technology, low cost, low pollution and the like.
Description
Technical field
The application belongs to semiconductor integrated circuit manufacturing process technology field, and particularly a kind of deep sub micrometer VLSI Cu interconnection film is the preparation method with double-deck high-entropy alloy diffusion impervious layer.
Background technology
Develop rapidly along with super large-scale integration (ULSI) Technology, unicircuit characteristic dimension continues to reduce, require diffusion impervious layer as far as possible when attenuate, maintain diffusion barrier performance and thermal stability under high temperature, this makes Al be on the rise as the problem of the RC delay device performance degradation that sharply increase causes of interconnection material generation.Even to this day, Cu progressively replaces Al as interconnecting metal material of new generation.Yet, although many physical propertiess of Cu self are applied in and have very large advantage on Si device it, but but there are some unavoidable problems in the application of Cu in Si device, as Cu has higher rate of diffusion in Si and oxide compound thereof, once Cu atom enters Si layer, at lower temperature, just can become deep energy level acceptor impurity, the current carrier in device is had to very strong trap effect, cause device performance degeneration, ultimate failure.In addition the adhesion property of Cu and medium a little less than, easily oxidized.Therefore, in Cu interconnection process, must introduce suitable metal or alloy rete with the adhesivity of Reinforced Cu and medium, play the diffusion reaction that stops Cu and Si simultaneously.
At present the research of Cu diffusion impervious layer is mainly concentrated on to the following aspects: (1) simple substance refractory metal and alloy material, as document [Khin Maung LATT, H.S.PARK, S.LI.Journal of Materials Science, 2002,37 (2002): 1941 – 1949] and [J.S.FANG, T.P.HSU, H.C.CHEN.2007, Journal ofElectronicMaterials, 36 (5): 614-622].Although indissoluble elemental metals and binary alloy have lower resistivity and with the advantage such as Cu adhesivity is better, its thermostability is generally poor, reacts with Si below to cause blocking layer to be lost efficacy at 600 ℃; (2) nitrogen/carbide of refractory metal and refractory metal ternary compound, as document [Khin MaungLatt, C.Sher-Yi, T.Osipowicz.Journal of Materials Science, 2001,36 (2001): 5705 – 5712] and [L.W.Lin, B.Liu, D.Ren et al.Surface and Coatings Technology.2012].Although refractory metal nitride and ternary compound have higher thermostability, because N, O, C under hot conditions easily diffuse to the interface of blocking layer and Cu, cause the adhesivity of blocking layer and Cu to reduce, cause the appearance of interfacial gap.
For overcoming the existing shortcoming of above-mentioned materials, seek novel material and novel process address the above problem imperative.In recent years, investigators turn one's attention to high-entropy alloy one after another, wish to utilize the good physics and chemistry performance that high-entropy alloy is had to address the above problem.
High-entropy alloy why have excellent physics and chemistry performance mainly depend on the effect that conventional alloys do not have [Ye Junwei. the development of high-entropy alloy. magnificent ridge engineering journal, 2011,27 (2011): 1-18].Investigator wishes that the high entropy effect that can utilize high-entropy alloy to have, serious lattice distortion effect are solving adhesivity, improves stability of material simultaneously, utilizes its slow diffusional effect, cocktail effect to improve the ability that diffusion impervious layer hinders diffusion.
Just because of high-entropy alloy has good diffusion barrier performance and thermostability, investigators are applied in high-entropy alloy and nitride thereof in Cu interconnection diffusion impervious layer one after another, and have obtained good effect.As the interconnection expansion blocking layer using 50nmAlCrTaTiZr nitride film as Cu, invalid temperature can reach 900 ℃ [Shou-Yi Chang, Ming-Ku Chen.Thin Solid Films, 2009,517 (2009): 4961 – 4965]; For meeting the requirement of diffusion impervious layer ultrathin, Chang has designed (AlCrRuTaTiZr) Nx diffusion impervious layer [Chang SY, Li C E, Huang Y C, Huang Y C.J Alloys Compd, 2012 that thickness is 4nm; 515:4].For reaching the object of improving diffusion impervious layer and metal level bonding properties, avoid because the difference of thermal expansion coefficients of nitride and Cu is larger, under high temperature, in interface, easily form cavity, cause metal interconnecting wires to lose efficacy, Chang and Chen etc. have designed (AlCrTaTiZr) N/ (AlCrTaTiZr) N0.7 bilayer diffusion barrier, but (AlCrTaTiZr) N0.7 has also increased the resistivity of system in the adhering while of improvement, make interconnection system postpone to increase [Chang S Y, Chen D S.MaterChem Phys, 2011; 125:5].
Summary of the invention
The state of the art and deficiency for double-deck high-entropy alloy diffusion impervious layer, the application's object aims to provide a kind of preparation method who is suitable for industrialized double-deck high-entropy alloy diffusion impervious layer, by the method, prepare prepare Heat stability is good, resistivity is low, and can improve and Cu between the double-deck high-entropy alloy diffusion impervious layer of adhesion property.
The application's basic thought is: first on Si matrix, first deposit one deck HEANs layer, its reason is: between (1) HEANs and Si matrix, have good adhesivity, can guarantee that diffusion impervious layer can not come off from Si matrix; (2) utilize the high thermal stability of HEANs layer, improve the invalid temperature of whole diffusion impervious layer.Then on HEANs layer, deposit the HEAs layer of one deck low-resistivity, produce HEAs/HEANs low-resistance bilayer diffusion barrier.Utilize the adhesivity that HEAs and Cu are good, improve the bonding properties of diffusion impervious layer and Cu, solve conventional nitride relative poor with the adhesivity of Cu, thereby cause the problem of the stability reduction of the system of interconnecting.The high entropy effect and the lattice distortion effect that due to high-entropy alloy self, have make HEAs/HEANs diffusion impervious layer can, due to the difference of thermal expansivity between metal and its nitride, not cause diffusion impervious layer to come off when device is on active service simultaneously.The application chooses Al, Cr, Ta, Ni, Ti for forming the starting material of high-entropy alloy, is to have good high entropy effect and lattice distortion effect because present inventor finds the high-entropy alloy material that AlCrTaNiTi forms.The application has also further studied how to obtain nano level HEANs and HEAs film, for meeting microelectronic product process requirements, provides development space.
The preparation method of the double-deck high-entropy alloy diffusion impervious layer that the application provides, mainly comprises following preparation process:
(1) single crystalline Si matrix is successively placed in respectively to acetone and dehydrated alcohol, carry out ultrasonic cleaning, be first placed in acetone or dehydrated alcohol carries out after ultrasonic cleaning, then be placed in dehydrated alcohol or acetone carries out ultrasonic cleaning, after fully cleaning, take out drying for standby.
The object of this step is to adopt ultrasonic oscillation method to remove the impurity such as the oil stain of single crystalline Si matrix surface, dust, can adopt the above-mentioned acetone providing and dehydrated alcohol as scavenging solution, also can take the organic solvent with same function as scavenging solution.Through fully cleaning, remove the impurity such as oil stain, dust of single crystalline Si matrix surface completely.Scavenging period is unimportant, as long as can reach the effect of abundant cleaning.In this application, single crystalline Si matrix is placed in acetone and dehydrated alcohol ultrasonic cleaning is no less than 20min successively.
(2) using single crystalline Si matrix with as Ta target, Al target, the Cr target of target, insert in magnetron sputtering plating vacuum oven, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet; After magnetron sputtering plating vacuum oven is vacuumized, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, adopt pre-sputtering to clean the impurity of removing in target and target sheet, reverse sputtering and pre-sputtering operation pressure are (1～3) Pa.
The object of this step is to carry out sputter clean to single crystalline Si matrix with as Ta target, Al target, Cr target, Ni target sheet, the Ti target sheet of target, further remove the impurity in single crystalline Si matrix and Ta target, Al target, Cr target, Ni target sheet, Ti target sheet, particularly above impurity atoms and the oxide skin of formation; The application does not have particular requirement to sputtering power, as long as can remove the impurity in single crystalline Si matrix and Ta target, Al target, Cr target, Ni target sheet, Ti target sheet.
It is (160～240) W that the single crystalline Si matrix reverse sputtering providing in the application cleans power, and bias voltage is (700～-800) V; Ta target, Al target, Cr target, Ni target sheet and Ti target sheet sputter clean power are (60～100) W.For other magnetron sputtering plating vacuum oven, reverse sputtering and pre-sputtering power can be adjusted to some extent.
For reverse sputtering and pre-sputtering operation pressure, be limited to (1～3) Pa, its reason is, for the magnetron sputtering plating vacuum oven of the application's employing, when pressure is less than 1Pa, can not reach the cleaning performance of reverse sputtering and pre-sputtering; When pressure is greater than 3Pa, will exceed equipment work scope.For other magnetron sputtering plating vacuum oven, the operation pressure of reverse sputtering and pre-sputtering can be adjusted to some extent, and this adjustment relies on the application's inventive concept, will fall into the application's protection domain.
The application does not have special requirement for the time of the reverse sputtering in this step and pre-sputtering, as long as can arrive above-mentioned sputter clean object, all can.Reverse sputtering scavenging period in this step that the application provides is (8～12) min, and pre-sputtering scavenging period is (10～15) min.
In order to guarantee that sputter clean maintains within the scope of operation pressure, can, before passing into Ar, vacuum in magnetron sputtering plating vacuum oven be evacuated to and be not less than 10
-3pa, more preferably 10
-4pa, so also can guarantee the cleaning quality to single crystalline Si matrix and Ta target, Al target, Cr target, Ni target sheet, Ti target sheet.
(3) using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs film of thickness, during sputter, pass into Ar and N
2, Ar and N
2throughput ratio be 1:(0.65～0.9), regulating deposition pressure is (0.3～0.6) Pa.
The object of this step is, the HEANs film of depositing and setting thickness on single crystalline Si matrix.In order to obtain above-mentioned HEANs film, need in magnetron sputtering plating vacuum oven, pass into N
2, and make the atomic ratio of high-entropy alloy AlCrTaTiNi and N be about 1:1, for this reason, need to control Ar and N
2throughput ratio be 1:(0.65～0.9); N
2when very few, can not guarantee that the atomic ratio of high-entropy alloy AlCrTaTiNi and N is about 1:1.Preferred Ar and N in the application
2throughput ratio be 1:0.75, further preferred Ar flow is 40sccm, N
2flow is 30sccm.
Regulating deposition pressure is in order to obtain thinner HEANs thin film layer, by regulating deposition pressure at (0.3～0.6) Pa, can obtaining, sets thickness for the HEANs film of (9～12) nm.
The application does not have particular requirement to deposition power, as long as can reach the atomic deposition on Ta target, Al target, Cr target, Ni target sheet and Ti target sheet to single crystalline Si matrix.The deposition sputtering power providing in the application is (60-100) W.For other magnetron sputtering plating vacuum oven, deposition sputtering power can be adjusted to some extent.
(4) HEANs thin film layer is deposited into design thickness, closes N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure (0.3～0.6) Pa, adopt pre-sputtering to clean and remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber.
The object of this step is to remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber, for next step obtains HEAs film, prepares.The HEAs film obtaining due to needs is nano level, if residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber is not processed, the double-deck high-entropy alloy diffusion impervious layer quality that impact finally obtains greatly, what even obtain is not the double-deck high-entropy alloy diffusion impervious layer that the application provides.
Here it should be noted that, the application is in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber are carried out to pre-sputtering cleaning, do like this, when having guaranteed double-deck high-entropy alloy diffusion impervious layer HEAs/HEANs performance, reduced the energy consumption producing because extract back end vacuum, greatly reduce production cost, be more suitable for suitability for industrialized production, and be easy to other microelectronics manufacture compatible mutually.
The application does not have particular requirement to sputtering power, as long as can remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber.The Ta target providing in the application, Al target, Cr target, Ni target sheet and Ti target sheet sputter clean power are (60-100) W.For other magnetron sputtering plating vacuum oven, reverse sputtering and pre-sputtering power can be adjusted to some extent.
In this step, for pre-sputtering operation pressure, be limited to (0.3～1) Pa, its reason is, for the magnetron sputtering plating vacuum oven of the application's employing, when pressure is less than 0.3Pa, can not reach the object of the cleaning of pre-sputtering; When pressure is greater than 1Pa, will increase the loss of target, increase cost.For other magnetron sputtering plating vacuum oven, the operation pressure of the pre-sputtering of this step can be adjusted to some extent, and this adjustment relies on the application's inventive concept, will fall into the application's protection domain.
The application does not have special requirement for the time of the pre-sputtering in this step, as long as can arrive above-mentioned sputter clean object, all can.Pre-sputtering scavenging period in this step that the application provides is 15～25min.
(5) take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness, during sputter, take Ar gas as working gas, and regulating deposition pressure is (0.3～0.6) Pa.
The object of this step is, continues the HEAs film that deposition one deck is set thickness on HEANs film.
In this step, take Ar as working gas, regulating deposition pressure lower is in order to obtain thinner HEANs film, by regulating deposition pressure at (0.3～0.6) Pa, can obtaining, sets thickness for the HEAs film of (9～12) nm.
The application does not have particular requirement to the deposition power of this step, as long as can reach the atomic deposition on Ta target, Al target, Cr target, Ni target sheet and Ti target sheet to HEANs film.The deposition sputtering power providing in the application is (60～100) W.For other magnetron sputtering plating vacuum oven, deposition sputtering power can be adjusted to some extent.
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, vacuum tightness in magnetron sputtering plating vacuum oven is adjusted to and is not less than 10
-3pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
In technique scheme, single crystalline Si matrix is preferably selected N-type single crystalline Si, and single crystalline Si matrix is oriented to [100].
In technique scheme, Al target purity is preferably not less than 99.95%, Cr target purity and is preferably not less than 99.95%, Ta target purity and is preferably not less than 99.95%, Ni sheet purity and is preferably not less than 99.95%, Ti purity and is preferably not less than 99.95%.
The preparation method of the double-deck high-entropy alloy diffusion impervious layer that the application provides has following beneficial effect:
1, the double-deck high-entropy alloy diffusion impervious layer HEAs/HEANs that prepared by the application, has improved the bonding strength on matrix, Cu and blocking layer, and improves the overall thermal stability of diffusion impervious layer.
2, the double-deck high-entropy alloy diffusion impervious layer HEAs/HEANs that prepared by the application utilizes the serious lattice distortion effect of high-entropy alloy, guarantees that the HEANs layer of preparation can be combined effectively with HEAs layer.
3, the application is in the process of the double-deck high-entropy alloy diffusion impervious layer HEAs/HEANs of preparation, do not change vacuum and target modes of emplacement, when guaranteeing double-deck high-entropy alloy diffusion impervious layer HEAs/HEANs performance, reduced the energy consumption producing because extract back end vacuum, greatly reduce production cost, be more suitable for suitability for industrialized production, and be easy to other microelectronics manufacture compatible mutually.
4, the double-deck high-entropy alloy diffusion impervious layer that prepared by the application, the size of HEANs thin film layer and HEAs thin film layer, below 12nm, can be good at meeting microelectronic product processing request, and provides development space for further reducing size.
5, the application's preparation method adopts Ni sheet and Ti sheet as raw material, not only can save the target position adopting in sputter procedure, for later further expanding and reserved space, and can save in sputter procedure for the saving of raw material, further saves cost.
6, the application's preparation method adopts popular response radiofrequency magnetron sputtering technology, the maturation that possesses skills, the feature such as cost is low, and pollutent is few.
Accompanying drawing explanation
Accompanying drawing described herein is to be used to provide further understanding of the present application, forms the application's a part, and the application's schematic description and description is used for explaining the application, but does not form the improper restriction to the application.
Fig. 1 schematically shows the structural representation of the film sample with double-deck high-entropy alloy diffusion impervious layer obtaining according to embodiment of the application; Wherein, 1-Cu layer, 2-HEAs layer, 3-HEANs layer, 4-Si matrix;
Fig. 2 schematically shows scanning electron microscope (SEM) Cross Section Morphology of the film sample with double-deck high-entropy alloy diffusion impervious layer obtaining according to embodiment of the application; Wherein, (a)-deposited, (b)-700 ℃ of annealed state, (c)-800 ℃ of annealed state, (d)-900 ℃ of annealed state;
Fig. 3 schematically shows scanning electron microscope (SEM) surface topography of the film sample with double-deck high-entropy alloy diffusion impervious layer obtaining according to embodiment of the application; Wherein, (a)-deposited, (b)-700 ℃ of annealed state, (c)-800 ℃ of annealed state, the enlarged view of (d)-900 ℃ of annealed state and black dotted lines part;
Fig. 4 schematically shows in Fig. 3 the thin film composition distribution collection of illustrative plates (EDS) of selection area in d figure; And
Fig. 5 schematically shows X ray diffracting spectrum under the different annealing temperature of the film sample with double-deck high-entropy alloy diffusion impervious layer obtaining according to embodiment of the application.
Embodiment
In order to make the application's object, technical scheme and advantage clearer, below in conjunction with specific embodiment, the application is described in further detail.
In the following description, the expression of quoting to " embodiment ", " embodiment ", " example ", " example " etc., described embodiment or example can comprise special characteristic, structure, characteristic, character, element or limit, but are not that each embodiment or example must comprise special characteristic, structure, characteristic, character, element or limit.In addition, reuse phrase " according to the application embodiment " and, although be likely to refer to identical embodiment, not must refer to identical embodiment.
Embodiment 1:
(1) crystal orientation is placed on to dehydrated alcohol and carries out respectively about 20min ultrasonic cleaning for the N-type single crystalline Si matrix of [100] is first placed in acetone, after fully cleaning, take out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet, wherein Ni target sheet and Ti target sheet only occupy the part position of Cr target and Ta target; Magnetron sputtering plating vacuum oven is evacuated to 4.0 * 10
-4after Pa, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, the power that reverse sputtering cleans is 200W, and bias voltage is-700V; Adopt pre-sputtering to clean the impurity of removing target and target sheet, the power that pre-sputtering is cleaned is 60W; Reverse sputtering and pre-sputtering operation pressure are 2Pa; Reverse sputtering scavenging period is about 10min, and pre-sputtering scavenging period is about 15min;
(3) after reverse sputtering cleaning and pre-sputtering are cleaned and are finished, using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness 10nm, during sputter, pass into Ar and N
2, Ar flow is 40sccm, N
2flow is 30sccm, and adjusting deposition pressure is 0.3Pa; Deposition sputtering power is 60W;
(4) HEANs thin film layer is deposited into design thickness, closes N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure 0.3Pa, adopt pre-sputtering to clean, remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber; Pre-sputtering power is 60W; The pre-sputtering time is about 20min;
(5) after in step (4), pre-sputtering cleaning finishes, take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness 10nm, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.3Pa; Deposition sputtering power is 60W;
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, make the vacuum tightness in magnetron sputtering plating vacuum oven be adjusted to 4.0 * 10
-4pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
In order to verify the performance of the double-deck high-entropy alloy diffusion impervious layer that the present invention obtains, after prepared by above-mentioned double-deck high-entropy alloy diffusion impervious layer, do not change under the condition of vacuum in magnetron sputtering plating vacuum oven chamber, adopt d.c. sputtering at double-deck high-entropy alloy diffusion impervious layer, to deposit the Cu layer (purity of Cu target is 99.95%) of 100nm on it, obtain having the film sample of double-deck high-entropy alloy diffusion impervious layer, wherein Ar operating air pressure is 0.6Pa, and sputtering power is 100W.The film sample with double-deck high-entropy alloy diffusion impervious layer of above-mentioned preparation is further divided into four groups, wherein one group is the deposited sample that the present embodiment provides, other three groups are carried out respectively high vacuum annealing, obtain 700 ℃ of annealing specimens, 800 ℃ of annealing specimens, 900 ℃ of annealing specimens.The base vacuum of vacuum annealing furnace is 2.0 * 10
-5pa, annealing temperature is 700 ℃, 800 ℃ or 900 ℃, annealing time is 30min,
Fig. 1 schematically shows the above-mentioned structural representation with the film sample of double-deck high-entropy alloy diffusion impervious layer.As shown in the figure, Si matrix 4 is in bottom, and Cu layer 1, topmost, is respectively HEAs layer 2 and HEANs layer 3 between Cu layer 1 and Si matrix 4, and HEAs2 is near Cu layer 1, and HEANs layer 3 is near Si matrix 4.
Fig. 2 schematically shows above-mentioned scanning electron microscope (SEM) Cross Section Morphology with the film sample of double-deck high-entropy alloy diffusion impervious layer.As can be seen from the figure, unannealed sample, system structure is complete, between double-deck high-entropy alloy diffusion impervious layer and Cu layer 1 and Si matrix 4, has good bonding force; The sample of 800 ℃ of following annealing, system structure is still very complete, between double-deck high-entropy alloy diffusion impervious layer and Cu layer 1 and Si matrix 4, still can keep good bonding force.The sample of 900 ℃ of annealing, the bonding force between double-deck high-entropy alloy diffusion impervious layer and Cu layer 1 and Si matrix 4 is destroyed.As can be seen here, the double-deck high-entropy alloy diffusion impervious layer that the preparation method who provides by the application obtains has good thermostability
Fig. 3 schematically shows above-mentioned scanning electron microscope (SEM) surface topography with the film sample of double-deck high-entropy alloy diffusion impervious layer.As can be seen from the figure the sample surfaces after 700 ℃, 800 ℃ annealing presents striated, there is certain crackle, and present certain fluctuating, striated is the result of Cu grain growth under high temperature annealing condition, further rising along with annealing temperature, due to thermal stresses and capillary effect, surface starts to present massif shape.And when temperature is elevated to 900 ℃, it is coarse and discontinuous that Cu surface topography starts to become, and in part, there is bright taper particle (seeing the part that dotted line frame provides).
Fig. 4 schematically shows in Fig. 3 the thin film composition distribution collection of illustrative plates (EDS) of selection area in d figure.Through the EDS energy spectrum analysis to taper particulate matter, find mainly to contain Cu and Si in particulate matter.In conjunction with the XRD spectrum after 900 ℃ of annealing, can confirm to have generated the Cu-Si phase of high-impedance state. illustrate that Cu/AlCrTaTiNi/ (AlCrTaTiNi) N/Si sample is in the time of 900 ℃, double-deck high-entropy alloy diffusion impervious layer is complete failure.
Fig. 5 schematically shows X ray diffracting spectrum under the different annealing temperature of the above-mentioned film sample with double-deck high-entropy alloy diffusion impervious layer.Result shows, along with the rising of annealing temperature, Cu (111) orientation obviously strengthens, and occurs with weak Cu (200) simultaneously.But after 900 ℃ of annealing, Cu (111) and Cu (200) disappear, and have occurred a large amount of Cu-Si phases, illustrate that now Cu, with Si, mutual diffusion has occurred, generated deep energy level phase, diffusion impervious layer inefficacy.
Embodiment 2:
(1) crystal orientation is placed on to acetone and carries out respectively about 30min ultrasonic cleaning for the N-type single crystalline Si matrix of [100] is first placed in dehydrated alcohol, after fully cleaning, take out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet, wherein Ni target sheet and Ti target sheet only occupy the part position of Cr target and Ta target; Magnetron sputtering plating vacuum oven is evacuated to 1.2 * 10
-4after Pa, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, the power that reverse sputtering cleans is 160W, and bias voltage is-800V; Adopt pre-sputtering to clean the impurity of removing target and target sheet, the power that pre-sputtering is cleaned is 100W; Reverse sputtering and pre-sputtering operation pressure are 1Pa; Reverse sputtering scavenging period is about 12min, and pre-sputtering scavenging period is about 10min;
(3) after reverse sputtering cleaning and pre-sputtering are cleaned and are finished, using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness 12nm, during sputter, pass into Ar and N
2, Ar flow is 40sccm, N
2flow is 36sccm, and adjusting deposition pressure is 0.6Pa; Deposition sputtering power is 80W;
(4), when HEANs thin film layer is deposited into design thickness, close N
2intake valve, in not changing magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure 1Pa, adopt pre-sputtering to clean, remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber; Pre-sputtering power is 80W; The pre-sputtering time is about 15min;
(5) after in step (4), pre-sputtering cleaning finishes, take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness 12nm, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.6Pa; Deposition sputtering power is 80W;
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, make the vacuum tightness in magnetron sputtering plating vacuum oven be adjusted to 1.0 * 10
-4pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
Embodiment 3:
(1) the N-type single crystalline Si matrix that is [100] by crystal orientation is placed in successively acetone and dehydrated alcohol carries out respectively about 25min ultrasonic cleaning, after fully cleaning, takes out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet, wherein Ni target sheet and Ti target sheet only occupy the upper part position of Cr target and Ta target; Magnetron sputtering plating vacuum oven is evacuated to 4.0 * 10
-4after Pa, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, the power that reverse sputtering cleans is 240W, and bias voltage is-700V; Adopt pre-sputtering to clean the impurity of removing target and target sheet, the power that pre-sputtering is cleaned is 80W; Reverse sputtering and pre-sputtering operation pressure are 3Pa; Reverse sputtering scavenging period is about 8min, and the pre-sputtering time is about 15min;
(3) after reverse sputtering cleaning and pre-sputtering are cleaned and are finished, using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness 9nm, during sputter, pass into Ar and N
2, Ar flow is 40sccm, N
2flow is 26sccm, and adjusting deposition pressure is 0.3Pa; Deposition sputtering power is 80W;
(4), when HEANs thin film layer is deposited into design thickness, close N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure 0.6Pa, adopt pre-sputtering to clean, remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber; The pre-sputtering time is about 20min;
(5) after in step (4), pre-sputtering cleaning finishes, take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness 9nm, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.3Pa; Deposition sputtering power is 80W;
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, make the vacuum tightness in magnetron sputtering plating vacuum oven be adjusted to 4.0 * 10
-4pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
Embodiment 4:
(1) the N-type single crystalline Si matrix that is [100] by crystal orientation is placed in successively acetone and dehydrated alcohol carries out respectively about 20min ultrasonic cleaning, after fully cleaning, takes out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet, wherein Ni target sheet and Ti target sheet only occupy the upper part position of Cr target and Ta target; Magnetron sputtering plating vacuum oven is evacuated to 4.0 * 10
-4after Pa, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, the power that reverse sputtering cleans is 200W, and bias voltage is-800V; Adopt pre-sputtering to clean the impurity of removing target and target sheet, the power that pre-sputtering is cleaned is 100W; Reverse sputtering and pre-sputtering operation pressure are 1.5Pa; Reverse sputtering scavenging period is about 9min, and pre-sputtering scavenging period is about 10min;
(3) after reverse sputtering cleaning and pre-sputtering are cleaned and are finished, using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness 10nm, during sputter, pass into Ar and N
2, Ar flow is 40sccm, N
2flow is 30sccm, and adjusting deposition pressure is 0.3Pa; Deposition sputtering power is 100W;
(4), when HEANs thin film layer is deposited into design thickness, close N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure 0.8Pa, adopt pre-sputtering to clean, remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber; The pre-sputtering time is 15min;
(5) after in step (4), pre-sputtering cleaning finishes, take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness 10nm, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.3Pa; Deposition sputtering power is 100W;
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, make the vacuum tightness in magnetron sputtering plating vacuum oven be adjusted to 4.0 * 10
-4pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
Embodiment 5:
(1) the N-type single crystalline Si matrix that is [100] by crystal orientation is placed in successively acetone and dehydrated alcohol carries out respectively about 30min ultrasonic cleaning, after fully cleaning, takes out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet, wherein Ni target sheet and Ti target sheet only occupy the upper part position of Cr target and Ta target; Magnetron sputtering plating vacuum oven is evacuated to 1.2 * 10
-4after Pa, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, the power that reverse sputtering cleans is 180W, and bias voltage is-700V; Adopt pre-sputtering to clean the impurity of removing target and target sheet, the power that pre-sputtering is cleaned is 80W; Reverse sputtering and pre-sputtering operation pressure are 1.5Pa; Reverse sputtering scavenging period is about 12min, and pre-sputtering scavenging period is about 15min;
(3) after reverse sputtering cleaning and pre-sputtering are cleaned and are finished, using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness 11nm, during sputter, pass into Ar and N
2, Ar flow is 40sccm, N
2flow is 30sccm, and adjusting deposition pressure is 0.45Pa; Deposition sputtering power is 100W;
(4), when HEANs thin film layer is deposited into design thickness, close N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure 0.45Pa, adopt pre-sputtering to clean, remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber; The pre-sputtering time is 25min;
(5) after in step (4), pre-sputtering cleaning finishes, take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness 11nm, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.45Pa; Deposition sputtering power is 100W;
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, make the vacuum tightness in magnetron sputtering plating vacuum oven be adjusted to 4.0 * 10
-4pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
Embodiment 6:
(1) the N-type single crystalline Si matrix that is [100] by crystal orientation is placed in successively acetone and dehydrated alcohol carries out respectively 40min ultrasonic cleaning, after fully cleaning, takes out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet, wherein Ni target sheet and Ti target sheet only occupy the upper part position of Cr target and Ta target; Magnetron sputtering plating vacuum oven is evacuated to 4.0 * 10
-4after Pa, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, the power that reverse sputtering cleans is 220W, and bias voltage is-800V; Adopt pre-sputtering to clean the impurity of removing target and target sheet, the power that pre-sputtering is cleaned is 80W; Reverse sputtering and pre-sputtering operation pressure are 2.5Pa; Reverse sputtering scavenging period is 8min, and pre-sputtering scavenging period is 15min;
(3) after reverse sputtering cleaning and pre-sputtering are cleaned and are finished, using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness 12nm, during sputter, pass into Ar and N
2, Ar flow is 40sccm, N
2flow is 36sccm, and adjusting deposition pressure is 0.45Pa; Deposition sputtering power is 80W;
(4), when HEANs thin film layer is deposited into design thickness, close N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure 0.45Pa, adopt pre-sputtering to clean, remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber; The pre-sputtering time is 20min;
(5) after in step (4), pre-sputtering cleaning finishes, take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the Si/HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness 12nm, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.45Pa; Deposition sputtering power is 80W;
(6) when HEAs thin film layer is deposited into design thickness, close Ta target, Al target, Cr target, Ni target sheet and Ti target sheet, close Ar intake valve, make the vacuum tightness in magnetron sputtering plating vacuum oven be adjusted to 4.0 * 10
-4pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
Claims (10)
1. a preparation method for double-deck high-entropy alloy diffusion impervious layer, is characterized in that, comprises the following steps:
(1) single crystalline Si matrix is successively placed in respectively to acetone and dehydrated alcohol, carries out ultrasonic cleaning, after fully cleaning, take out drying for standby;
(2) single crystalline Si matrix step (1) being cleaned and inserting in magnetron sputtering plating vacuum oven as Ta target, Al target, the Cr target of target, and on Cr target, place Ni target sheet, on Ta target, place Ti target sheet; After magnetron sputtering plating vacuum oven is vacuumized, pass into Ar as working gas, adopt reverse sputtering to clean and remove impurity in single crystalline Si matrix, adopt pre-sputtering to clean the impurity of removing in target and target sheet, reverse sputtering and pre-sputtering operation pressure are 1～3Pa;
(3) using the cleaned Ta target of step (2) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet as magnetic controlling target, on the cleaned single crystalline Si matrix of step (2) reverse sputtering, adopt magnetron sputtering deposition to set the HEANs thin film layer of thickness, during sputter, pass into Ar and N
2, Ar and N
2throughput ratio be 1:(0.65～0.9), regulating deposition pressure is (0.3～0.6) Pa;
(4) HEANs thin film layer is deposited into design thickness, closes N
2intake valve, in not disrumpent feelings magnetron sputtering plating vacuum oven under vacuum condition, pass into Ar as working gas, in air pressure (0.3～1) Pa, adopt pre-sputtering to clean and remove residual N atom in Ta target, Al target, Cr target, Ni target sheet, Ti target sheet and magnetron sputtering plating vacuum oven chamber;
(5) take the cleaned Ta target of step (4) pre-sputtering, Al target, Cr target, Ni target sheet and Ti target sheet is magnetic controlling target, on the HEANs thin film layer obtaining in step (3), adopt magnetron sputtering deposition to set the HEAs thin film layer of thickness, during sputter, take Ar gas as working gas, and adjusting deposition pressure is 0.3～0.6Pa;
(6) when HEAs thin film layer is deposited into design thickness, close Ar intake valve, vacuum tightness in magnetron sputtering plating vacuum oven is adjusted to and is not less than 10
-3pa, comes out of the stove after naturally cooling and obtains double-deck high-entropy alloy diffusion impervious layer.
2. the preparation method of double-deck high-entropy alloy diffusion impervious layer according to claim 1, is characterized in that, described single crystalline Si matrix is N-type single crystalline Si matrix, and single crystalline Si matrix is oriented to [100].
3. the preparation method of double-deck high-entropy alloy diffusion impervious layer according to claim 1, is characterized in that, in step (1), single crystalline Si matrix is placed in acetone and dehydrated alcohol ultrasonic cleaning is no less than 20min.
4. the preparation method of double-deck high-entropy alloy diffusion impervious layer according to claim 1, is characterized in that, Al target purity is not less than 99.95%, Cr target purity is not less than 99.95%, Ta target purity is that 99.95%, Ni sheet purity is that 99.95%, Ti purity is 99.95%.
5. the preparation method of double-deck high-entropy alloy diffusion impervious layer according to claim 1, is characterized in that, by magnetron sputtering plating vacuum oven is evacuated to and is not less than 10
-4pa, to guarantee that sputter clean and sputtering sedimentation maintain within the scope of operation pressure.
6. according to the preparation method of the arbitrary described double-deck high-entropy alloy diffusion impervious layer of claim 1 to 5, it is characterized in that, the Ar flow passing in step (3) is 40sccm, N
2flow is 30sccm.
7. according to the preparation method of the arbitrary described double-deck high-entropy alloy diffusion impervious layer of claim 1 to 5, it is characterized in that, it is (160～240) W that described single crystalline Si matrix reverse sputtering cleans power, and bias voltage is (700～-800) V.
8. according to the preparation method of the arbitrary described double-deck high-entropy alloy diffusion impervious layer of claim 1 to 5, it is characterized in that, Ta target, Al target, Cr target, Ni target sheet and Ti target sheet sputter clean power are (60～100) W.
9. according to the preparation method of the arbitrary described double-deck high-entropy alloy diffusion impervious layer of claim 1 to 5, it is characterized in that, Ta target, Al target, Cr target, Ni target sheet and Ti target sheet magnetron sputtering deposition sputtering power are (60～100) W.
10. according to the preparation method of the arbitrary described double-deck high-entropy alloy diffusion impervious layer of claim 1 to 5, it is characterized in that, the setting thickness of HEANs film and HEAs film is (9～12) nm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264116A (en) * | 2014-09-25 | 2015-01-07 | 四川理工学院 | Process for preparing AlTiCrNiTa high-entropy alloy coating on surface of X80 pipeline steel base material |
| CN104911556A (en) * | 2015-05-02 | 2015-09-16 | 四川理工学院 | Preparation technology for Ni submicron arrays |
| CN108018550A (en) * | 2016-11-04 | 2018-05-11 | 叶均蔚 | multi-layer film structure |
| CN109989001A (en) * | 2019-04-09 | 2019-07-09 | 西安交通大学 | A kind of method of pulsed laser deposition technique preparation high rigidity infusibility high-entropy alloy film |
| CN109988998A (en) * | 2019-04-09 | 2019-07-09 | 西安交通大学 | A kind of preparation method of polynary high-entropy alloy film |
| CN111441026A (en) * | 2020-05-14 | 2020-07-24 | 南京工业大学 | Preparation method of high-entropy alloy with dual-phase structure |
| CN112064024A (en) * | 2020-09-23 | 2020-12-11 | 广东省科学院新材料研究所 | Diffusion-resistant high-entropy alloy coating material, high-temperature-resistant coating material, and preparation method and application thereof |
| CN114032502A (en) * | 2021-11-23 | 2022-02-11 | 江西省科学院应用物理研究所 | Wear-resistant corrosion-resistant composite layer and preparation method thereof |
| CN114783980A (en) * | 2022-06-21 | 2022-07-22 | 亚芯半导体材料(江苏)有限公司 | Multilayer alloy diffusion impervious layer for Cu interconnection integrated circuit and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060797A (en) * | 2013-01-14 | 2013-04-24 | 北京工业大学 | Preparation method of plasma cladding high-entropy alloy coating layer |
| CN103173716A (en) * | 2013-04-15 | 2013-06-26 | 上海电机学院 | High-entropy alloy coating preparation technology of tool die |
| CN103290404A (en) * | 2013-05-06 | 2013-09-11 | 浙江工业大学 | Laser-cladding high-entropy alloy powder and preparation method of high-entropy alloy coating |
| CN103757631A (en) * | 2014-01-27 | 2014-04-30 | 沈阳大学 | Preparation method of high-entropy AlCoNiCrFeMo alloy coating |
-
2014
- 2014-05-05 CN CN201410186108.4A patent/CN103966566B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060797A (en) * | 2013-01-14 | 2013-04-24 | 北京工业大学 | Preparation method of plasma cladding high-entropy alloy coating layer |
| CN103173716A (en) * | 2013-04-15 | 2013-06-26 | 上海电机学院 | High-entropy alloy coating preparation technology of tool die |
| CN103290404A (en) * | 2013-05-06 | 2013-09-11 | 浙江工业大学 | Laser-cladding high-entropy alloy powder and preparation method of high-entropy alloy coating |
| CN103757631A (en) * | 2014-01-27 | 2014-04-30 | 沈阳大学 | Preparation method of high-entropy AlCoNiCrFeMo alloy coating |
Non-Patent Citations (2)
| Title |
|---|
| 张立东 等: "AlCrTaTiNi/(AlCrTaTiNi)N双层扩散阻挡层的制备及热稳定性", 《金属学报》 * |
| 彭佳 等: "多主元高熵合金涂层的研究进展", 《表面技术》 * |
Cited By (12)
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|---|---|---|---|---|
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| CN104911556A (en) * | 2015-05-02 | 2015-09-16 | 四川理工学院 | Preparation technology for Ni submicron arrays |
| CN104911556B (en) * | 2015-05-02 | 2018-04-17 | 四川理工学院 | A kind of preparation process of Ni submicron arrays |
| CN108018550A (en) * | 2016-11-04 | 2018-05-11 | 叶均蔚 | multi-layer film structure |
| CN108018550B (en) * | 2016-11-04 | 2019-12-03 | 叶均蔚 | Multi-layer film structure |
| CN109989001A (en) * | 2019-04-09 | 2019-07-09 | 西安交通大学 | A kind of method of pulsed laser deposition technique preparation high rigidity infusibility high-entropy alloy film |
| CN109988998A (en) * | 2019-04-09 | 2019-07-09 | 西安交通大学 | A kind of preparation method of polynary high-entropy alloy film |
| CN111441026A (en) * | 2020-05-14 | 2020-07-24 | 南京工业大学 | Preparation method of high-entropy alloy with dual-phase structure |
| CN112064024A (en) * | 2020-09-23 | 2020-12-11 | 广东省科学院新材料研究所 | Diffusion-resistant high-entropy alloy coating material, high-temperature-resistant coating material, and preparation method and application thereof |
| CN112064024B (en) * | 2020-09-23 | 2021-08-31 | 广东省科学院新材料研究所 | Diffusion-resistant high-entropy alloy coating material, high-temperature-resistant coating material, and preparation method and application thereof |
| CN114032502A (en) * | 2021-11-23 | 2022-02-11 | 江西省科学院应用物理研究所 | Wear-resistant corrosion-resistant composite layer and preparation method thereof |
| CN114783980A (en) * | 2022-06-21 | 2022-07-22 | 亚芯半导体材料(江苏)有限公司 | Multilayer alloy diffusion impervious layer for Cu interconnection integrated circuit and preparation method thereof |
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