CN114959397B - Alloy target material, preparation method and application thereof, and array substrate - Google Patents

Alloy target material, preparation method and application thereof, and array substrate Download PDF

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CN114959397B
CN114959397B CN202210470591.3A CN202210470591A CN114959397B CN 114959397 B CN114959397 B CN 114959397B CN 202210470591 A CN202210470591 A CN 202210470591A CN 114959397 B CN114959397 B CN 114959397B
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alloy target
layer
target material
motinicu
alloy
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CN114959397A (en
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宋智辉
王辉
康报虹
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HKC Co Ltd
Changsha HKC Optoelectronics Co Ltd
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Changsha HKC Optoelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate

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Abstract

The application relates to the field of semiconductor devices, and discloses an alloy target material, a preparation method and application thereof, and an array substrate. In order to further improve the characteristics of the Mo alloy barrier layer, mo, ti, ni and Cu are used as metal elements to prepare the MoTiNiCu alloy target material which can be applied to the field of semiconductors, the grain size of the alloy target material is less than 100 mu m and is superior to the current 120 mu m technical level, the sputtering efficiency is higher, and the compactness and the uniformity are better; meanwhile, the MoTiNiCu alloy target material has excellent oxidation resistance, adhesion, high temperature resistance and high humidity resistance; the metal diffusion of the wiring layer can be effectively blocked by matching with the wiring layer, and the etching performance of the metal diffusion blocking film has obvious advantages compared with that of the MoTiNi alloy.

Description

Alloy target material, preparation method and application thereof, and array substrate
Technical Field
The application relates to the field of semiconductor devices, in particular to an alloy target material, a preparation method and application thereof, and an array substrate.
Background
In the semiconductor industry, in order to reduce the resistance of wiring layers in flat display devices (FDPs) such as electrophoretic displays used in Liquid Crystal Displays (LCDs), plasma Display Panels (PDPs), and electronic papers, and in order to reduce the resistance of thin film electronic components such as various semiconductor devices, thin film sensors, and magnetic heads, al and Cu are generally used as conductive layers.
However, the heating process in the process of manufacturing the wiring layer of each component can cause severe Cu diffusion, and the adhesion between the Cu layer and the substrate is also poor, so that a metal barrier layer (barrier layer) is required to perform the transition and blocking functions. Transition layer metals are generally required to have excellent resistance to high temperature, high humidity and oxidation, excellent barrier properties against Cu diffusion, low coefficient of thermal expansion, and excellent etching properties. At present, the resistance of a common Mo metal layer is low, but the oxidation resistance of pure Mo is poor, the high temperature diffusion resistance cannot reach expectation, in addition, mo is easy to generate a reverse etching angle (taper) when being used as a barrier layer, the profile of a Mo/Cu layer is poor, an etching profile (profile) is unstable under high Cu ion concentration, and the fluctuation of critical dimension deviation (CD bias) is large.
Patent CN104046947A provides a Mo alloy sputtering target for metal thin film formation for use in laminating a coating film of a wiring layer, and proposes that the alloy sputtering target can improve moisture resistance and oxidation resistance, but it can be seen from the relevant experimental data described in the patent that the high temperature and high humidity resistance under the condition of 85 ℃ &85%rh still has a certain defect, and there is room for further improvement.
In addition, patent CN112941473A also discloses a MoTiNi alloy target, which is mainly applied to thin film electrodes or thin film wiring materials of flat panel displays such as LCD and PDP, so as to meet the requirements for large-sized, high-density, high-purity and non-magnetic targets, but it does not provide clear technical guidance on whether it is suitable for barrier layer metal as Cu layer, and actually explores that MoTiNi alloy target is poor in adhesion and etching performance as Cu transition layer.
Based on this, excellent high temperature and high humidity resistance, oxidation resistance, etching performance, and high adhesion performance with a Cu layer are urgent demands for metals of a metal barrier layer (barrier layer).
Disclosure of Invention
In view of the above, an object of the present invention is to provide an alloy target and a method for preparing the same, so that the alloy target has excellent high-temperature Cu layer diffusion resistance and excellent etching resistance, and is suitable for both high and low Cu ion concentrations when being overlapped with a Cu layer wiring layer.
In order to solve the above technical problems, or to achieve at least one of the above objects, the present application provides an alloy target material, which is a MoTiNiCu alloy target material, wherein, in atomic number percentage, mo is 50% to 70%, ti is 20% to 30%, ni is 5% to 29%, and Cu is 0.01% to 2%. In certain embodiments of the present application, the atomic percentages of Mo, ti, ni, and Cu are 50%, 22-26%, 23-27%, and 1%, respectively.
Based on the excellent performance of the alloy target, the application of the alloy target in the preparation of an array substrate is provided. The array substrate is provided with a Cu layer wiring layer.
Meanwhile, the application also provides a preparation method of the alloy target, wherein alloy powder and/or pure metal powder which are mixed to form the MoTiNiCu alloy target are subjected to powder sintering to obtain the MoTiNiCu alloy target.
In addition, in some embodiments of the present application, an array substrate based on the alloy target described herein is further provided, and includes a substrate, a gate electrode, a gate insulating layer, a channel layer, a source electrode, and a drain electrode, wherein the gate electrode and the gate insulating layer are disposed on the substrate, the gate insulating layer covers the gate electrode, and a metal barrier layer (barrier layer) formed by the alloy target is disposed between the gate electrode and the substrate and/or the gate insulating layer; and arranging a channel layer on the gate insulating layer, wherein a source electrode and a drain electrode are arranged on the channel layer.
In some other embodiments of the present application, the array substrate further includes a metal barrier layer (barrier layer) formed by the alloy sputtering target between the source electrode and the channel layer and between the drain electrode and the channel layer.
Compared with the existing similar alloy target, the MoTiNiCu alloy target has the following beneficial effects: (1) The average grain size of the alloy target material is less than 100 mu m, the fluctuation of the resistance and the visible light reflectivity after single-film high-temperature oxidation is small, the visible light reflectivity is not obviously changed under the conditions of 85 ℃ and 85 percent RH, the thickness and the number of the surface oxidation layer are small, and the surface adhesion is gradually enhanced along with the increase of the oxidation temperature;
(2) When the copper-clad laminate is compounded with a Cu wiring layer, after high-temperature vacuum annealing, the interface of a film layer is clear, the element dispersion is reduced after thermal diffusion, and copper diffusion can be effectively blocked; the etching performance can be more excellent under the ion concentration of 500-10000ppm Cu.
Drawings
FIG. 1 is a schematic structural diagram of an array substrate; 1 denotes a glass substrate, 2 denotes a gate electrode to which a metal barrier layer of the present application is added, and is referred to as an M1 layer in the present application; 3 denotes a G-SiNx gate insulating layer; 4 represents an a-Si layer, 5 represents N + a-Si layer, the two layers form a channel layer; 6 a source electrode and a drain electrode, referred to herein as an M2 layer, to which a metal barrier layer of the present application is added;
FIG. 2 is a flow chart of the process for preparing the MoTiNiCu alloy target material of the present application; wherein CIP represents cold isostatic pressing, HIP represents hot isostatic pressing, and Bonding represents binding;
FIG. 3 shows the surface morphology of the MoTiNiCu alloy target film after oxidation;
FIG. 4 is a schematic diagram of an EDS line scan of the MoTiNiCu/Cu composite layer of the present application;
FIG. 5 is a graph showing the EDS elemental distribution of the cross section of the MoTiNiCu/Cu composite layer of the present application;
FIG. 6 is a cross-sectional profile of a control MoTiNi alloy target after etching; magnification times 60000;
FIG. 7 is a cross-sectional view of the MoTiNiCu alloy target of the present application after etching; magnification x 60000.
Detailed Description
The application discloses an alloy target material, a preparation method, application and an array substrate thereof, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which are obvious to those skilled in the art are deemed to be incorporated herein by reference. While the products, processes and applications described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products, processes and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this application without departing from the content, spirit and scope of the application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all embodiments. 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 application.
It is noted that, in this document, relational terms such as "first" and "second", "step 1" and "step 2", and "(1)" and "(2)" may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising one of 8230; \8230;" 8230; "does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element. Meanwhile, the embodiments and features in the embodiments may be combined with each other in the present application without conflict.
The MoTiNiCu alloy target material provided by the invention has excellent high-temperature Cu layer diffusion resistance and excellent etching capability, and can solve any one or more of the following problems:
the MoTiNiCu alloy target material provided by the invention can enable the average grain size of the alloy target material to be less than 100 mu m, thereby realizing higher sputtering efficiency and better compactness and uniformity;
the MoTiNiCu alloy target material provided by the invention can enable the alloy target material to have excellent high-temperature and high-humidity resistance;
the MoTiNiCu alloy target material provided by the invention can enable the alloy target material to have excellent oxidation resistance;
the MoTiNiCu alloy target material provided by the invention can enable the alloy target material to have excellent adhesion;
in each set of comparative experiments provided in the present application, unless otherwise specified, other experimental conditions, materials, etc. are kept consistent for comparability, except for the differences indicated for each set.
The following further describes an alloy target material, a preparation method, an application and an array substrate thereof provided by the present application.
The first embodiment: alloy target material and preparation process thereof
1. Alloy target material
The embodiment of the application provides a MoTiNiCu alloy target, which comprises: mo, ti, ni and Cu, wherein the atomic number percentage content of each metal element is as follows: 50 to 70 percent of Mo, 20 to 30 percent of Ti, 5 to 29 percent of Ni and 0.01 to 2 percent of Cu.
In an alternative embodiment of the present application, mo is 50%, ti is 22-26%, ni is 23-27%, and Cu is 1%.
2. Preparation process
The MoTiNiCu alloy target material can be prepared by a powder sintering process, wherein in the powder sintering process, metal raw material powder is mixed by a grinding stirring or gas atomization method, and the metal raw material powder can adopt a pressure sintering mode such as hot isostatic pressing, hot pressing, spark plasma sintering, extrusion pressing sintering and the like;
for example, the preparation process of the alloy target material is completed by grinding and stirring mixed metal raw material powder, cold isostatic pressing primary forming, machining into a die, hot isostatic pressing pressure sintering, machining, binding and shipment procedures, and the process flow chart is shown in fig. 2;
the specific preparation process of the alloy target material comprises the following steps:
1) The respective atomic number percentages of the metal elements were as described in the present example by mixing the powders of the MoTi alloy (1 μm to 100 μm, purity 99%), the powder of the MoNi alloy (1 μm to 100 μm, purity 99%), and the powder of the Cu alloy (1 μm to 100 μm, purity 99%);
2) The mill stirs for 10-100 min to fully mix the powder in the protective gas.
3) Loading into special container, covering and sealing, cold isostatic pressing to prepare rough blank, the pressure is 50-400 MPa, and the time is 10-60 min.
4) Taking out the rough blank, grinding and performing primary die forming;
5) The hot isostatic pressing treatment is further compact, and the hot isostatic pressing condition is as follows: the temperature is 1000-1400 ℃, the time is 1-8 h, and the pressure is 50-300 MPa;
6) Further grinding the primary die;
7) And (binding) shipment.
The MoTiNiCu metal rotary target prepared according to the preparation process is deposited on a glass substrate through a PVD (Physical Vapor Deposition) coating to prepare two samples of MoTiNiCu (60 nm) and MoTiNiCu/Cu (30 nm/400 nm), and the samples are subjected to performance tests such as oxidation resistance, moisture resistance, adhesion and the like by combining the use environment of an LCD (Liquid Crystal Display) wiring layer:
MoTiNiCu (60 nm) single film results show:
(1) The relative density of the characteristics of the prepared target material is more than or equal to 99.5 percent, the purity is more than 99.5 percent, the average grain size is less than 100 mu m, the binding rate (binding Ratio) is more than or equal to 97 percent, the related indexes are superior to those of the same industry, the smaller the grain size of the target material is, the higher the sputtering efficiency is, and the better the compactness and the uniformity are;
(2) The MoTiNiCu single-film oxidation property is stable, and the resistance change rate is less than 7.28% after the MoTiNiCu single-film oxidation is carried out for 1 hour at 300 ℃; the change rate of the reflection of the visible light surface is less than 8.0 percent, the surface oxidation appearance at 450 ℃ has no color change, no oxidation cavity and no oxidation peeling phenomenon;
(3) Stable against high temperature and high humidity, a surface reflection change of < 5% after standing for 200h under 85 ℃ &85 RH (relative humidity);
(4) After the film is oxidized for 1 hour at the temperature of RT-450 ℃, the adhesive force of the film after being oxidized is not reduced, the surface adhesive property is gradually enhanced along with the increase of the oxidation temperature, and the grain size and the stress distribution on the surface are changed along with the increase of the temperature, so that the adhesive force is enhanced;
MoTiNiCu/Cu (30 nm/4000 nm) composite coating results show that:
(1) The interface of the film layer with the section of 1h after high vacuum annealing at 350 ℃ is clear, the element dispersion degree is reduced after thermal diffusion, and copper diffusion can be effectively blocked;
(2) The surface of the MoTiNiCu/Cu coating has no residue after being etched, and the taper (etching angle) of samples of the M1 layer and the M2 layer after being etched has good stability and smaller fluctuation, which is superior to the MoTiNi/Cu coating; in the M2 layer sample, the Cu ion concentration is from 500ppm → 10000ppm, and the fluctuation of CD bias (Critical Dimension bias) formed after etching is smaller and is better than that of the MoTiNi/Cu coating.
Second embodiment: mo 50 Ti 22 Ni 27 Cu alloy target material, preparation thereof and single-film performance and composite coating performance detection
1. Mo 50 Ti 22 Ni 27 Cu alloy target material
The MoTiNiCu alloy target comprises 50% of Mo, 22% of Ti, 27% of Ni and 1% of Cu in atomic percentage;
2. preparation process
1) Mixing MoTi alloy powder (1-100 μm, purity 99%), moNi alloy powder (1-100 μm, purity 99%), cu powder (1-100 μm, purity 99%), mo (at%): 50%; ti (at%): 22 percent; ni (at%): 27 percent; 1 percent of Cu (at percent);
2) The powder is fully mixed in protective gas by stirring for 10-100 min by a grinder.
3) Loading in special container, covering and sealing, cold isostatic pressing to prepare coarse blank at 50-400 MPa for 10-60 min.
4) Taking out the rough blank, grinding and shaping by a primary die;
5) The hot isostatic pressing treatment is further compact, and the hot isostatic pressing condition is as follows: the temperature is 1000-1400 ℃, the time is 1-8 h, and the pressure is 50-300 MPa;
6) Further grinding the primary mould;
7) And (binding) shipment.
3. Mo 50 Ti 22 Ni 27 Cu (60 nm) single-film performance detection
1. Oxidability
(1) Resistance (RC)
The resistance change after oxidation for 1h at different temperatures is tested by using a film resistance tester, and the result shows that the resistance change rate is less than 7.28% after oxidation for 1h at 300 ℃, the result after film oxidation is not changed greatly, the number of formed oxides is less, and the resistance fluctuation of the MoTiNiCu film after high-temperature oxidation is smaller (Table 2);
TABLE 2
Oxidation temperature (. Degree. C.) 25 200 300
Square resistance (omega/\ 9633;) 21.43 20.63 22.99
Rate of change 0.00％ -3.73％ 7.28％
(2) Visible light reflectance
Measuring resistance change of the film layer after oxidation for 1h at different temperatures by using a light splitting test, wherein the result shows that the surface reflectivity change is less than 8.0 percent (compared with 25 ℃) after oxidation for 1h at 300 ℃, and the film layer does not change color with naked eyes, has no oxidation cavity and has no oxidation peeling phenomenon after being oxidized at 450 ℃; the MoTiNiCu film has small thickness and quantity of the surface oxide layer (Table 3 and figure 3);
TABLE 3
Figure BDA0003621763400000061
2. High temperature moisture resistance
After the film is placed for 100h and 200h under the condition of 85 ℃ plus 85 percent RH and the visible light reflection characteristic of the film is detected by a spectrometer, the surface reflection change rate is basically unchanged after 200h (compared with room temperature RT), and the thickness and the number of the surface oxide layers are also shown to be small after the MoTiNiCu film double 85 experiment (Table 4);
TABLE 4
Temperature of RT 100h 200h
Reflectance (%) 45.46 45.72 45.67
3. Adhesion test
The absolute normal force of the film after being oxidized for 1 hour at different temperatures is measured by a nanometer scratch tester, the film is oxidized for 1 hour at RT-450 ℃, the adhesive force of the oxidized film is not reduced, the surface adhesive property is gradually enhanced along with the increase of the oxidation temperature, and the grain size and the stress distribution on the surface are changed by the increase of the temperature, so that the adhesive force is enhanced (Table 5);
TABLE 5
Figure BDA0003621763400000062
4. Mo 50 Ti 22 Ni 27 Cu/Cu (30 nm/4000 nm) composite coating performance detection
1. MoTiNiCu/Cu high temperature diffusion resistance
After the sample is subjected to high vacuum annealing at 350 ℃ for 1h, EDS element diffusion analysis is carried out on the section, and the result shows that the interface of the film layer is clear, the element dispersion degree is reduced after thermal diffusion, and copper diffusion can be effectively blocked (fig. 4 and fig. 5).
2. MoTiNiCu/Cu etch characterization
Combining the application of MoTiNiCu in LCD products, depositing MoTiNiCu/Cu film layers on different substrates to prepare film layer samples (refer to fig. 1) of M1 and M2 with different substrates, forming linear patterns by a PHOTO lithography (PHOTO) process, and then performing etching experiments under different Cu ion concentrations; simultaneous preparation of Mo 51 Ti 22 Ni 27 the/Cu coatings were etch-controlled and the results show (Table 6 and FIGS. 6-7):
under different Cu ion concentrations, the fluctuation of taper and CD bias is large after MoTiNi/Cu coating M1 and M2 samples are etched, and residues appear at the etching corner tails; an M1 layer sample, wherein the Cu ion concentration is 500ppm → 5000ppm, and a taper angle (52 ° → 41 °) is formed after etching; m2 layer sample, cu ion concentration from 500ppm → 10000ppm, CD bias formed after etching (698 nm → 369 nm);
the stability of the etched taper of the MoTiNiCu/Cu coating M1 and M2 samples is good, and the angle range of the etched taper is (31-38 ℃); the concentration of Cu ions of the M2 layer sample is 500ppm → 10000ppm, and the CD bias formed after etching (845 nm → 613 nm) is better than that of a MoTiNi/Cu coating (698 nm → 369 nm);
in the practical use process, the Cu concentration in the Cu etching solution is gradually increased due to the cyclic use of the Cu etching solution, the decomposition of hydrogen peroxide is accelerated in the solution due to the increase of the Cu ion concentration, so that the etching rate of the MoTiNiCu/Cu layer is slowed down, the fact that the MoTiNiCu/Cu layer maintains a stable etching rate in the hydrogen peroxide fluctuation range is crucial, and the result of the etching experiment shows that the MoTiNiCu/Cu composite coating has excellent etching performance and is superior to the MoTiNi/Cu composite coating.
TABLE 6
Figure BDA0003621763400000071
Note: based on the data of fig. 6-7, rounding.
The third embodiment: mo 50 Ti 24 Ni 25 Preparation of Cu alloy target and detection of single-film performance and composite coating performance of Cu alloy target
1. Mo 50 Ti 24 Ni 25 Cu alloy target material
The MoTiNiCu alloy target comprises 50% of Mo, 24% of Ti, 25% of Ni and 1% of Cu in atomic percentage;
2. preparation process
1) Mixing MoTi alloy powder (1-100 μm, purity 99%), moNi alloy powder (1-100 μm, purity 99%), cu powder (1-100 μm, purity 99%), mo (at%): 50%; ti (at%): 24 percent; ni (at%): 25 percent; 1% of Cu (at%);
2) The powder is fully mixed in protective gas by stirring for 10-100 min by a grinder.
3) Loading in special container, covering and sealing, cold isostatic pressing to prepare coarse blank at 50-400 MPa for 10-60 min.
4) Taking out the rough blank, grinding and shaping by a primary die;
5) The hot isostatic pressing treatment is further compact, and the hot isostatic pressing condition is as follows: the temperature is 1000-1400 ℃, the time is 1-8 h, and the pressure is 50-300 MPa;
6) Further grinding the primary die;
7) And (binding) shipment.
3. Mo 50 Ti 24 Ni 25 Cu (60 nm) single-film performance detection
(1) The relative density of the characteristics of the prepared target material is more than or equal to 99.5 percent, the purity is more than 99.5 percent, the average grain size is less than 100 mu m, the binding rate (binding Ratio) is more than or equal to 97 percent, the related indexes are superior to those of the same industry, the smaller the grain size of the target material is, the higher the sputtering efficiency is, and the better the compactness and the uniformity are;
(2) The MoTiNiCu single-film oxidation property is stable, and the resistance change rate is less than 7.5% after the MoTiNiCu single-film oxidation is carried out for 1h at 300 ℃; the change rate of the reflection of the visible light surface is less than 8.5 percent, the surface oxidation appearance at 450 ℃ has no color change, no oxidation cavity and no oxidation peeling phenomenon;
(3) High temperature and high humidity resistance, the percentage of change of surface reflection is less than 5 percent after the alloy is placed under the condition of 85 ℃ and 85 percent RH for 200 hours;
(4) After the film is oxidized for 1 hour at the temperature of RT-450 ℃, the adhesive force of the film after being oxidized is not reduced, the surface adhesive property is gradually enhanced along with the increase of the oxidation temperature, and the grain size and the stress distribution on the surface are changed along with the increase of the temperature, so that the adhesive force is enhanced;
4. mo 50 Ti 24 Ni 25 Cu/Cu (30 nm/4000 nm) composite coating performance detection
(1) The interface of the film layer with the section of 1h after high vacuum annealing at 350 ℃ is clear, the element dispersion degree becomes small after thermal diffusion, and copper diffusion can be effectively blocked;
(2) The surface of the MoTiNiCu/Cu coating has no residue after being etched, and the taper (etching angle) of samples of the M1 layer and the M2 layer after being etched has good stability and smaller fluctuation, which is superior to the MoTiNi/Cu coating; in the M2 layer sample, the Cu ion concentration is from 500ppm → 10000ppm, and the fluctuation of CD bias (Critical Dimension bias) formed after etching is smaller and is better than that of the MoTiNi/Cu coating.
The fourth embodiment: mo 50 Ti 26 Ni 23 Preparation of Cu alloy target and detection of single-film performance and composite coating performance of Cu alloy target
1. Mo 50 Ti 26 Ni 23 Cu alloy target material
The MoTiNiCu alloy target comprises 50% of Mo, 26% of Ti, 23% of Ni and 1% of Cu in atomic percentage;
2. preparation process
1) MoTi alloy powder (1-100 mu m, purity 99%), moNi alloy powder (1-100 mu m, purity 99%), cu powder (1-100 mu m, purity 99%) are mixed, and Mo (at%) is 50%; ti (at%): 26 percent; ni (at%): 23 percent; 1 percent of Cu (at percent);
2) The mill stirs for 10-100 min to fully mix the powder in the protective gas.
3) Loading into special container, covering and sealing, cold isostatic pressing to prepare rough blank, the pressure is 50-400 MPa, and the time is 10-60 min.
4) Taking out the rough blank, grinding and shaping by a primary die;
5) The hot isostatic pressing treatment is further compact, and the hot isostatic pressing condition is as follows: the temperature is 1000-1400 ℃, the time is 1-8 h, and the pressure is 50-300 MPa;
6) Further grinding the primary die;
7) And (binding) shipment.
3. Mo 50 Ti 26 Ni 23 Cu (60 nm) single-film performance detection
(1) The relative density of the characteristics of the prepared target material is more than or equal to 99.5 percent, the purity is more than 99.5 percent, the average grain size is less than 100 mu m, the binding rate (binding Ratio) is more than or equal to 97 percent, the related indexes are superior to those of the same industry, the smaller the grain size of the target material is, the higher the sputtering efficiency is, and the better the compactness and the uniformity are;
(2) The MoTiNiCu single-film oxidation property is stable, and the resistance change rate is less than 7.8% after the MoTiNiCu single-film oxidation is carried out for 1 hour at 300 ℃; the change rate of the reflection of the visible light surface is less than 8.2 percent, the surface oxidation appearance at 450 ℃ has no color change, no oxidation cavity and no oxidation peeling phenomenon;
(3) Stable against high temperature and high humidity, a change in surface reflection of < 5% after standing for 200h under 85 ℃ & 85%;
(4) After the film is oxidized for 1 hour at the temperature of RT-450 ℃, the adhesive force of the film after being oxidized is not reduced, the surface adhesive property is gradually enhanced along with the increase of the oxidation temperature, and the grain size and the stress distribution on the surface are changed along with the increase of the temperature, so that the adhesive force is enhanced;
4. mo 50 Ti 26 Ni 23 Performance detection of Cu/Cu (30 nm/4000 nm) composite coating
(1) The interface of the film layer with the section of 1h after high vacuum annealing at 350 ℃ is clear, the element dispersion degree becomes small after thermal diffusion, and copper diffusion can be effectively blocked;
(2) The surface of the MoTiNiCu/Cu coating has no residue after being etched, and the taper (etching angle) of samples of the M1 layer and the M2 layer after being etched has good stability and smaller fluctuation, which is superior to the MoTiNi/Cu coating; in the M2 layer sample, the Cu ion concentration is from 500ppm → 10000ppm, and the fluctuation of CD bias (Critical Dimension bias) formed after etching is smaller and is better than that of the MoTiNi/Cu coating.
Fifth embodiment: array substrate based on MoTiNiCu alloy target material
The related application of the alloy target material, mainly used as a metal barrier layer of a wiring layer, also called a barrier layer, is particularly applied to a component aiming at a Cu layer wiring layer, and the application field comprises but is not limited to a liquid crystal display, a plasma display, a flat panel display, a thin film electronic component and the like. Where thin film electronic components are involved, this includes, but is not limited to, various semiconductor devices, thin film sensors, and magnetic heads.
The application specifically provides an array substrate according to the application field, and the array substrate is applied to the performance detection of the alloy target composite coating in each embodiment, the structure is basically as shown in fig. 1, a grid electrode 2 added with a metal barrier layer is arranged on a glass substrate 1 and is called an M1 layer, the M1 layer is a MoTiNiCu/Cu composite layer, and the MoTiNiCu layer is positioned between a Cu layer and the glass substrate; the M1 layer is coated by a G-SiNx insulating layer 3, and an a-Si layer 4 and N are sequentially arranged on the G-SiNx insulating layer 3 from bottom to top + a-Si layer 5, both collectively referred to as a channel layer; said N is + a source electrode and a drain electrode 6 of a MoTiNiCu/Cu composite layer are arranged on the a-Si layer 5, which are collectively called M2 layer, wherein the MoTiNiCu layer is positioned on the Cu layer and the N layer + a-Si layer 5.
The array substrate can be applied to various display panels, including but not limited to liquid crystal display panels, organic light emitting display panels, miniLED display panel lamps, and the like.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. An alloy target material is a MoTiNiCu alloy target material which comprises, by atomic number percentage,
50% of Mo, 22-26% of Ti, 23-27% of Ni and 1% of Cu.
2. The alloy target according to claim 1, wherein the atomic percentages of Mo, ti, ni and Cu are 50%, 22%, 27% and 1%, respectively.
3. The alloy target according to claim 1, wherein the atomic percentages of Mo, ti, ni and Cu are 50%, 24%, 25% and 1%, respectively.
4. The alloy target according to claim 1, wherein the atomic percentages of Mo, ti, ni and Cu are 50%, 26%, 23% and 1%, respectively.
5. Use of an alloy target according to any one of claims 1 to 4 for the preparation of an array substrate.
6. The use of claim 5, wherein the array substrate has a Cu layer wiring layer.
7. The preparation method of the alloy target material, wherein the MoTiNiCu alloy target material is obtained by mixing alloy powder and/or pure metal powder which form the MoTiNiCu alloy target material according to any one of claims 1 to 4 and performing powder sintering.
8. An array substrate comprises a substrate, a gate electrode, a gate insulating layer, a channel layer, a source electrode and a drain electrode, wherein the gate electrode and the gate insulating layer are arranged on the substrate, the gate electrode is wrapped by the gate insulating layer, and a metal blocking layer formed by the alloy target material according to any one of claims 1 to 4 is arranged between the gate electrode and the substrate and/or the gate insulating layer; and arranging a channel layer on the gate insulating layer, wherein a source electrode and a drain electrode are arranged on the channel layer.
9. The array substrate of claim 8, further comprising a metal barrier layer formed of the alloy target according to any one of claims 1 to 4, disposed between the source electrode and the channel layer, and between the drain electrode and the channel layer, simultaneously or alternatively.
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