CN108573856B - Preparation method and cleaning solution of array substrate - Google Patents

Preparation method and cleaning solution of array substrate Download PDF

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CN108573856B
CN108573856B CN201810333856.9A CN201810333856A CN108573856B CN 108573856 B CN108573856 B CN 108573856B CN 201810333856 A CN201810333856 A CN 201810333856A CN 108573856 B CN108573856 B CN 108573856B
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copper
cleaning solution
pattern layer
benzotriazole
amine
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CN108573856A (en
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刘三泓
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • 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
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1288—Multistep manufacturing methods employing particular masking sequences or specially adapted masks, e.g. half-tone mask
    • 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
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1296—Multistep manufacturing methods adapted to increase the uniformity of device parameters

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  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The invention provides a cleaning solution for cleaning a passivation film comprising a copper-benzotriazole complex on an array substrate, wherein the cleaning solution comprises water, inorganic base, organic amine and a copper chelating agent; the pH value of the cleaning liquid is 10-11; the chelating ability of the copper chelating agent and copper is greater than that of benzotriazole and copper, and a water-soluble complex can be generated; the organic amine is used for breaking coordination bonds in the copper-benzotriazole complex and dissolving benzotriazole. The cleaning solution is mainly used for cleaning the array substrate after a photoresist pattern layer is stripped by photoresist stripping solution containing benzotriazole. The invention also provides application of the cleaning solution in preparation of an array substrate.

Description

Preparation method and cleaning solution of array substrate
Technical Field
The invention relates to the technical field of display, in particular to a preparation method and cleaning solution of an array substrate.
Background
A Thin Film Transistor Liquid Crystal Display (TFT-LCD) has the characteristics of small volume, low power consumption, no radiation, and the like, and occupies a leading position in the current flat panel Display market. With the continuous development of TFT-LCD, the requirements for resistance and electron mobility are higher and higher, and in order to make TFT-LCD have higher contrast and image display quality, at present, low-resistance metal copper is usually used as a conductive material for manufacturing conductive patterns such as source and drain electrodes, source electrodes, gate lines, data lines, and the like. That is, the copper process (depositing a copper metal film and then etching it into a desired pattern) is gradually progressing in the field of TFT-LCD.
Benzotriazole (BTA) is generally adopted as a corrosion inhibitor of a photoresist stripping solution in a Cu process at present, and the BTA can be adsorbed on the surface of metal copper to form a passivation film containing a conductive complex (copper-BTA) and has an anti-corrosion effect on the copper in the photoresist stripping process. However, the copper-BTA is difficult to remove, and its residue may have a great influence on the stability of the display device, especially when Cu particles remain in a channel (e.g. a channel between a source and a drain) of a conductive pattern on a substrate of the display device, the copper-BTA may also adhere to the Cu particles in the channel (as shown in fig. 1) after being treated by a photoresist stripping solution of a Cu process, which greatly affects the electrical property of the display device.
Disclosure of Invention
In view of this, the invention provides a cleaning solution for cleaning a passivation film containing a copper-benzotriazole complex on an array substrate and a preparation method of the array substrate, so as to prevent residual substances such as copper-BTA in a channel of a conductive pattern of the array substrate from affecting the quality of the array substrate.
Specifically, the invention provides a preparation method of an array substrate, which comprises the following steps:
providing a substrate, and sequentially forming a semiconductor layer, a metal copper pattern layer and a light resistance pattern layer on one surface of the substrate;
carrying out dry etching on the semiconductor layer positioned in the channel of the metal copper pattern layer, and forming copper particles in the channel of the metal copper pattern layer; the channel of the metal copper pattern layer is a part of the semiconductor layer which is not covered by the metal copper pattern layer;
stripping the photoresist pattern layer by photoresist stripping liquid containing benzotriazole, wherein a passivation film is formed on the metal copper pattern layer and in a channel of the metal copper pattern layer in the stripping process, and the passivation film comprises a copper-benzotriazole complex;
cleaning the substrate with the photoresist pattern layer stripped by adopting a cleaning solution to remove the passivation film to obtain an array substrate; wherein the cleaning solution comprises water, inorganic base, organic amine and a copper chelating agent; the pH value of the cleaning liquid is 10-11; the chelating ability of the copper chelating agent and copper is greater than that of benzotriazole and copper, and a water-soluble complex can be generated with copper; the organic amine is used for breaking coordination bonds in the copper-benzotriazole complex and dissolving benzotriazole.
Wherein the copper chelator comprises one or more of disodium ethylenediaminetetraacetate (EDTA-disodium), diethylenetriaminepentaacetic acid sodium salt (DTPA pentasodium), iminodisuccinic acid sodium salt (IDS-tetrasodium), and sodium diethyldithiocarbamate (DDTC sodium salt).
Wherein the organic amine comprises alcohol amine, amide, short-chain aliphatic amine, aromatic amine and nitrogen heterocyclic substances. Further, the alcohol amine substance comprises one or more of monoethanolamine, diethanolamine and triethanolamine; the amide substances comprise one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA) and N-methylpyrrolidone (NMP); the nitrogen heterocyclic substance comprises piperidine, piperazine, imidazole, pyridine, piperidine and pyrrolidine; examples of the aromatic amine include benzylamine; the short-chain aliphatic amine comprises three methylamine (monomethylamine, dimethylamine and trimethylamine), monoethylamine, diethylamine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1, 2-propylenediamine, hexamethylenediamine and the like.
Wherein the organic amine is one or more of N, N-dimethylformamide, N-dimethylacetamide, triethanolamine and diethanolamine.
Wherein the inorganic base comprises one or more of NaOH, KOH and ammonia water.
Wherein, in the cleaning solution, the mass fraction of the copper chelating agent is 1-4%.
Wherein, in the cleaning solution, the mass fraction of the organic amine is 2-8%.
Wherein, in the cleaning solution, the mass fraction of the inorganic base is 0.5-2%.
Wherein, after the cleaning with the cleaning solution, the method further comprises: and depositing a protective layer on the metal copper pattern layer and the area of the semiconductor layer which is not covered by the metal copper pattern layer.
The semiconductor device further comprises a grid electrode and a grid electrode insulating layer which are sequentially stacked and arranged on the substrate, wherein the grid electrode and the grid electrode insulating layer are arranged between the semiconductor layer and the substrate; the metal copper pattern layer includes a source electrode and a drain electrode disposed on the semiconductor layer in the same layer.
Wherein the semiconductor layer includes a first silicon film and a second silicon film sequentially provided on the substrate; wherein the first silicon film is amorphous silicon containing no impurity; the second silicon film is amorphous silicon doped with N-type impurities.
The second silicon film comprises a source contact region and a drain contact region which are arranged at intervals, the source contact region is positioned below the source electrode, and the drain contact region is positioned below the drain electrode.
According to the preparation method of the array substrate, the array substrate after a photoresist pattern layer is stripped by adopting a photoresist stripping liquid containing BTA is cleaned by adopting a cleaning liquid containing water, inorganic base, organic amine and a copper chelating agent and having a pH value of 10-11, wherein the inorganic base, the organic amine and the copper chelating agent are hydrophilic substances, the inorganic base and the organic amine jointly provide a proper alkaline environment, and under the alkaline environment, the chelating capacity of the copper chelating agent and copper is greater than that of benzotriazole and copper, and a water-soluble complex can be generated; the organic amine is used for softening a passivation film, breaking a coordination bond of the copper-benzotriazole complex and dissolving benzotriazole. Therefore, the cleaning solution can well remove the passivation film (including Cu particles, copper-BTA and the like) formed on the metal copper pattern layer and in the photoresist stripping process in the channel of the metal copper pattern layer, and the cleaning solution does not affect the structure on the array substrate, particularly does not cause conductive residues between the channels of the metal copper pattern layer to affect the electrical property of the subsequent array substrate.
The invention also provides a cleaning solution for cleaning the passivation film comprising the copper-benzotriazole complex on the array substrate, wherein the cleaning solution comprises water, inorganic base, organic amine and a copper chelating agent; the pH value of the cleaning liquid is 10-11; the chelating ability of the copper chelating agent and copper is greater than that of benzotriazole and copper, and a water-soluble complex can be generated with copper; the organic amine is used for breaking coordination bonds in the copper-benzotriazole complex and dissolving benzotriazole. Wherein, the components in the cleaning solution are as described above. The cleaning solution is mainly used for cleaning the array substrate after a photoresist pattern layer is stripped by adopting a photoresist stripping solution containing BTA.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is a schematic structural diagram of an array substrate before and after stripping with a photoresist stripper in a copper process according to the prior art; 10 is a substrate, 20 is a semiconductor layer, 30 is an initial copper film, 30a is an etched metal copper pattern layer, 40 is a light resistance pattern layer, and 30b is a passivation film;
fig. 2 is a flowchart of a method for manufacturing an array substrate according to an embodiment of the invention;
fig. 3 is a schematic structural view of the substrate in fig. 1 (D) after being cleaned in step S03;
FIG. 4 is a schematic diagram illustrating the formation of a passivation layer on the substrate after the cleaning in step S03 according to an embodiment of the present invention;
FIG. 5 is a schematic structural diagram of a substrate before and after dry etching in step S02 according to another embodiment of the present invention;
fig. 6 is a process of forming an array substrate with a gate pattern according to another embodiment of the present invention.
Fig. 7 is a schematic view illustrating a manufacturing process of an array substrate according to another embodiment of the present invention.
Detailed Description
Referring to fig. 1, fig. 1 is a schematic structural diagram of an array substrate before and after stripping with a photoresist stripper in a copper process in the prior art. In FIG. 1B, the initial copper film 30 is etched (e.g., using H) using the resist pattern layer 40 of FIG. 1A as a mask2O2Wet etching) is performed, a copper metal pattern layer 30, which may be a source electrode and a drain electrode, is obtained. In fig. 1 (C), the semiconductor layer 20 in the channel of the substrate in fig. 1 (B) is dry-etched to thin the semiconductor layer 20, leaving only the regions that can be contacted with the source and drain, which can be referred to as a source contact region and a drain contact region, respectively. It should be noted that, when the semiconductor layer 20 is dry-etched, since the etching gas used in the dry etching is bombarded onto the metallic copper pattern layer 30 during the etching process, Cu particles (indicated by arrows (C) in fig. 1) generated by the bombardment remain on the semiconductor layer 20 in the trenches of the metallic copper pattern layer 30 a.
In FIG. 1, (D) the resist pattern layer 40 is stripped using a resist stripper, leaving the copper metal pattern layer 30. The photoresist stripper solution generally used in this step contains Benzotriazole (BTA) to prevent corrosion of copper during stripping of the photoresist 40. The mechanism of corrosion prevention is roughly as follows: BTA can be adsorbed on the surface of metallic copper to form a stable passive film with the structure of Cu/Cu2O/Cu (I) -BTA. Therefore, in the photoresist stripping process, the copper metal pattern layer 30a and the semiconductor layer 20 remainThe surfaces of the remaining Cu particles are covered with a passivation film 30 b. The Cu (I) -BTA in the passivation film is relatively stable, is difficult to dissolve in common organic solvents and has conductivity. Particularly, the passivation film remaining at the circle (D) in fig. 1 has conductivity, which causes conduction of the copper metal pattern layer 30 (for example, conduction between adjacent source and drain), which greatly interferes with the electrical property of a display device manufactured by using the substrate at a later stage, and thus affects the display quality.
In view of the above problem, referring to fig. 2, a method for manufacturing an array substrate according to an embodiment of the present invention is described below, including:
s01, providing a substrate 10, and sequentially forming a semiconductor layer 20, a copper metal pattern layer 30a and a photoresist pattern layer 40 on one surface of the substrate 10 (as shown in fig. 1 (B));
s02, dry etching the semiconductor layer 20 in the channel of the metal copper pattern layer 30a (as shown in (C) of fig. 1), forming copper particles in the channel of the metal copper pattern layer 30 a; the channel of the metal copper pattern layer 30a is a portion of the semiconductor layer 20 not covered by the metal copper pattern layer 30 a;
s03, stripping the photoresist pattern layer 40 by using photoresist stripping liquid containing benzotriazole; a passivation film 30b is formed on the metal copper pattern layer 30a and in the channel of the metal copper pattern layer 30a in the stripping process (as shown in fig. 1 (D)), and the material of the passivation film 30b includes a Cu (i) -BTA conductive complex;
s04, cleaning the substrate with the photoresist pattern layer stripped off by adopting a cleaning solution to remove the passivation film to obtain an array substrate; the cleaning solution comprises: water, inorganic base, organic amine and copper chelating agent; the pH value of the cleaning solution is 10-11.
The operations in steps S01, S02, and S03 are substantially the same as described in fig. 1. Some details are explained below.
In step S01, the material of the substrate 1 is not limited, and may be a glass substrate, a flexible substrate, or the like. In step S01, the copper metal pattern layer 30a does not entirely cover the semiconductor layer 20, i.e., the stacked structure of the copper metal pattern layer 30a and the photoresist pattern layer 40 is disposed on the semiconductor layer 20 at an interval. The metallic copper pattern layer 30a may include a source electrode, a drain electrode, a data line, etc.
In step S02, the dry etching is performed on the portion of the semiconductor layer 20 not covered by the metallic copper pattern layer 30 a. The purpose of the dry etching is to thin the semiconductor layer 20 between the channels of the copper metal pattern layer 30a and remove the conductive portions thereof, leaving only conductive regions that can be in contact with the source and drain electrodes, which can be referred to as source and drain contact regions, respectively.
As shown in fig. 5, in one embodiment of the invention, the substrate structure before and after the dry etching in step S02 is schematically illustrated. The copper metal pattern layer 30a may specifically include a copper source 31 and a copper drain 32. The semiconductor layer 20 includes a first silicon film 21 and a second silicon film 22 provided in this order on the substrate 10; wherein the first silicon film 21 is amorphous silicon (a-Si) containing no impurity and serves as a channel of a transistor; the second silicon film 22 is amorphous silicon (N) doped with N-type impurities+a-Si). The second silicon film 22 between the copper source 31 and the copper drain 32 is removed by etching the semiconductor layer 20 between the trenches of the metallic copper pattern layer 30a, and the first silicon film 21 in the trenches is also thinned to a thickness of about 0.05-0.1 μm. The etched semiconductor layer 20 is a thinned first silicon film 21, and a source contact region 221 (source contact region) and a drain contact region 222 which are located on both ends of the first silicon film 21 and are in contact with the source and the drain, respectively.
Optionally, the etching gas used in the dry etching includes a fluorine-containing gas and hydrogen. Further, the fluorine-containing gas includes CF4、NF3And SF6At least one of (1).
In the cleaning solution used in the step S04, the chelating ability of the copper chelating agent to copper is greater than that of benzotriazole to copper, and the copper chelating agent can form a water-soluble complex with copper, so that the copper chelating agent can be conveniently removed by washing with water. The organic amine is mainly used for softening the passivation film, breaking coordinate bonds in the copper-benzotriazole complex (copper-BTA) and dissolving benzotriazole substituted by the copper chelating agent. The organic amine also has some basicity. The inorganic base is mainly used for providing an alkaline environment, so that the copper chelating agent and the organic amine can better play a role.
The inorganic base, the organic amine and the copper chelating agent are hydrophilic substances. Optionally, the copper chelator comprises one or more of disodium ethylenediaminetetraacetic acid (EDTA-disodium), diethylenetriaminepentaacetic acid sodium salt (DTPA pentasodium), iminodisuccinic acid sodium salt (IDS-tetrasodium), and sodium diethyldithiocarbamate (DDTC sodium salt).
Optionally, the organic amine comprises alcamines, amides, short-chain aliphatic amines, aromatic amines, nitrogen-containing heterocyclic substances. Further, the alcohol amine substance comprises one or more of monoethanolamine, diethanolamine and triethanolamine; the amide substances comprise one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA) and N-methylpyrrolidone (NMP); the nitrogen heterocyclic substance comprises piperidine, piperazine, imidazole, pyridine, piperidine and pyrrolidine; examples of the aromatic amine include benzylamine; the short-chain aliphatic amine comprises three methylamine (monomethylamine, dimethylamine and trimethylamine), monoethylamine, diethylamine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1, 2-propylenediamine, hexamethylenediamine and the like.
Further preferably, the organic amine is one or more of N, N-dimethylformamide, N-dimethylacetamide, triethanolamine, and diethanolamine.
Optionally, the inorganic base comprises one or more of NaOH, KOH, and ammonia.
Optionally, in the cleaning solution, the mass fraction of the copper chelating agent is 1-4%. For example, 1.2%, 1.5%, 2%, 2.5%, 3%, or 3.5%.
Optionally, in the cleaning solution, the mass fraction of the organic amine is 2-8%. For example 2.5%, 3%, 4%, 5%, 6%, 7% or 8%.
Optionally, in the cleaning solution, the mass fraction of the inorganic base is 0.5-2%. For example 0.6%, 0.8%, 1%, 1.2%, 1.5% or 2%.
Optionally, the pH of the cleaning solution is 10, 10.2, 10.5, 10.6, 10.8, or 11.
Further optionally, the cleaning solution is a mixed solution of water, NaOH (1 wt%), organic amine (5 wt%), and copper chelating agent (wt%), wherein the pH of the cleaning solution is 10.5, the organic amine is DMF, and the copper chelating agent is EDTA-disodium.
The array substrate after the photoresist pattern layer 40 is stripped is cleaned by using the above cleaning solution containing water, inorganic base, organic amine and copper chelating agent and having a pH of 10-11, and a structural schematic diagram of the cleaned substrate is shown in FIG. 3. Obviously, the passivation film 30b formed in the photoresist stripping process on the metal copper pattern layer 30a and the passivation film 20b (including Cu particles, copper-BTA, etc.) formed in the photoresist stripping process of the semiconductor layer 20 between the trenches of the metal copper pattern layer 30a are removed well, and the surface roughness of the substrate is reduced well.
Optionally, after the cleaning with the cleaning solution in step S03, the preparation method further includes:
s05, depositing a protection layer 50 on the copper pattern layer 30a and the semiconductor layer in the area not covered by the copper pattern layer 30a, and the structure of the array substrate is shown in fig. 4. The material of the protection layer 50 is an insulating protection material, such as a single layer of silicon nitride (SiNx) or a single layer of silicon oxide (SiOx), or a stack of silicon oxide (SiOx) and silicon nitride (SiNx). Optionally, the thickness of the protective layer 5 is
Figure BDA0001628667260000071
The protective layer 50 may be made by deposition and patterning processes. The deposition process includes Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD). Wherein the CVD process includes, but is not limited to, hot filament chemical vapor deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), and the like. PVD methods include, but are not limited to, magnetron sputtering, vacuum evaporation, ion plating (e.g., arc ion plating, radio frequency ion plating), and the like. Preferably, the protective film is formed by CVD. The patterning process is a technique of removing a portion of the complete material layer to form a desired structure in the remaining portion of the material layer, and generally includes one or more steps of coating, exposing to a mask, baking, developing, etching, and peeling.
Alternatively, in another embodiment of the present invention, the array substrate before being cleaned with the cleaning solution provided herein is a bottom gate type, as shown in fig. 7 (h), wherein between the substrate 10 and the semiconductor layer 20, the method further includes: the gate electrode 2 'and the gate insulating layer 3' disposed on the substrate 10 are sequentially stacked. The above-mentioned metal copper pattern layer specifically includes here the source electrode 31 and the drain electrode 32 disposed on the semiconductor layer 20 in the same layer. The source electrode 31 and the drain electrode 32 are respectively provided with a photoresist pattern 41 to be stripped. The semiconductor layer 20 here includes the first silicon film 21, and the source contact region 221 and the drain contact region 222 located on both ends of the first silicon film 21, as shown in fig. 5 (B) described above.
The method for manufacturing the array substrate of fig. 7 is used to illustrate the technical solution of the present invention.
S10, preparing the array substrate of fig. 7 (h), including:
s11, referring to fig. 6, forming a pattern including a gate electrode 2' on the substrate 10 by using a patterning process;
s12, referring to fig. 7 (e), sequentially depositing a gate insulating layer (GI)3 ', a semiconductor layer 20, and a second metallic copper film layer M2 on the substrate 1 formed with the gate pattern 2', and then forming a photoresist pattern 41 using a gray tone mask;
s13, wet etching off the second copper metal film M2 outside the trench, and ashing with oxygen plasma to remove the photoresist (i.e., the thinnest part of the photoresist pattern 41) inside the trench, thereby forming the structure shown in FIG. 7 (f);
s14, dry etching the semiconductor layer 20 and the GI layer 3' outside the channel, and etching the second metal copper film M2 in the channel by wet etching process to form the isolated source 31 and drain 32, forming the structure (g) in FIG. 7;
s15, and etching the semiconductor 20 layer in the trench by dry etching to form the structure (h) in fig. 7.
Wherein, step S11 specifically includes the following steps: referring to fig. 6, a first metal film M1 is deposited on a substrate by sputtering or thermal evaporation, and then a photoresist is coated on the surface of the first metal film M1, and a photoresist pattern 4' as shown in fig. 6 (b) is selectively formed by exposure, development and photolithography using a first mask. Then, M1 is etched using the resist pattern 4' as a mask, and the resist is stripped to form gate and gate line patterns. This step is similar to (A), (B), (D) in FIG. 1. The gate electrode and the gate line are formed in the same pattern and position as those of the related art in the display area (AA area) of the array substrate. And the metal film existing in the non-display area of the array substrate may still be referred to as M1.
In step S11, the gate pattern may be a patterned layer made of copper. After stripping the photoresist, the substrate may be cleaned by the cleaning solution to remove the passivation film on the surface of the gate 2'; the cleaning process may be omitted, which is mainly to make the area of the substrate not covered by the gate 2 'have almost no copper particles before the photoresist 4' is stripped, and accordingly no passivation film is formed in the area, which hardly affects the electrical property of the subsequent device. Further, the cleaning solution is a mixed solution of water, NaOH (1 wt%), organic amine (5 wt%) and a copper chelating agent (wt%), wherein the pH of the cleaning solution is 10.5, the organic amine is DMF, and the copper chelating agent is EDTA-disodium.
In step S12, the GI layer 3', the semiconductor layer 2 may be deposited by Chemical Vapor Deposition (CVD), and the second metallic copper film M2 may be deposited by Physical Vapor Deposition (PVD). The second metallic copper film layer M2 in fig. 7 (e) corresponds to 30 in fig. 1.
The semiconductor layer 20 of fig. 7 (f) or the semiconductor layer 20 of fig. 7 (g) located under the source and drain electrodes 31 and 32 includes: the whole surface mentioned in fig. 5 covers the first silicon film 21 on the GI layer 3', and the whole surface covers the second silicon film 22 of the first silicon film 21.
In step S14, H may be used to wet etch the second cu film M2 in the trench2O2To proceed with.
In step S15, the etching gas used in the dry etching includes a fluorine-containing gas and hydrogen. Further, the fluorine-containing gas includes CF4And SF6At least one of (1).
S20, stripping the photoresist in fig. 7 (h) with a photoresist stripper containing BTA to form the structure in fig. 7 (i) (the passivation film formed during stripping is not specifically shown here).
S30, washing the array substrate in fig. 7 (i) with the specific washing solution provided by the present application to obtain an array substrate without a passivation film on the copper thin film.
The cleaning solution used in step S30 may be a mixed solution of water, NaOH (1 wt%), organic amine (5 wt%), and copper chelating agent (wt%), wherein the pH of the cleaning solution is 10.5, the organic amine is DMF, and the copper chelating agent is EDTA-disodium.
Through the cleaning of the cleaning solution provided by the embodiment of the invention, in the array substrate, the copper-containing BTA passive film formed on the metal copper pattern layer and in the channel of the metal copper pattern layer (residual Cu particles) in the photoresist stripping process is well removed, and the cleaning solution does not influence the structure on the array substrate, particularly does not enable conductive residues to exist between the channels of the metal copper pattern layer to influence the electrical property of the subsequent array substrate, and simultaneously well reduces the surface roughness of the substrate. Of course, the cleaning solution provided by the present invention is not limited to the above application, and after the resist pattern on the copper metal pattern layer (including the gate electrode, the gate line (scanning line), the source electrode, the drain electrode, the data line, and the like) in the array substrate is stripped with the BTA-containing resist stripping solution, the cleaning solution provided by the present invention can be used to perform cleaning treatment, thereby efficiently removing the passivation film. The area of the array substrate to be cleaned is not limited to its visible area (AA area, left side of (i) in fig. 7) but may include a non-AA area (rightmost side of (i) in fig. 7).
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A cleaning solution is used for cleaning a passivation film on an array substrate, wherein the passivation film comprises a copper-benzotriazole complex, and is characterized in that the cleaning solution comprises water, inorganic base, organic amine and a copper chelating agent; the pH value of the cleaning liquid is 10-11; the chelating ability of the copper chelating agent and copper is greater than that of benzotriazole and copper, and a water-soluble complex can be generated with copper; the organic amine is used for breaking coordination bonds in the copper-benzotriazole complex and dissolving benzotriazole; wherein the organic amine comprises at least one of alcohol amine, amide, short-chain aliphatic amine, aromatic amine and nitrogen heterocyclic substance.
2. The cleaning solution according to claim 1, wherein the mass fraction of the copper chelating agent in the cleaning solution is 1-4%; the mass fraction of the organic amine is 2-8%, and the mass fraction of the inorganic base is 0.5-2%.
3. The cleaning solution of claim 1, wherein the copper chelating agent comprises disodium ethylenediaminetetraacetate, pentasodium diethylenetriaminepentaacetate, sodium iminodisuccinate salt, or sodium diethyldithiocarbamate;
the inorganic base comprises one or more of NaOH, KOH and ammonia water;
wherein, the alcohol amine substance comprises one or more of monoethanolamine, diethanolamine and triethanolamine; the amide substances comprise one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the nitrogen heterocyclic substance comprises one or more of piperidine, piperazine, imidazole, pyridine, piperidine and pyrrolidine; the aromatic amine comprises benzylamine; the short-chain aliphatic amine comprises one or more of monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1, 2-propylenediamine and hexamethylenediamine.
4. A preparation method of an array substrate is characterized by comprising the following steps:
providing a substrate, and sequentially forming a semiconductor layer, a metal copper pattern layer and a light resistance pattern layer on one surface of the substrate;
performing dry etching on the semiconductor layer in the channel of the metal copper pattern layer, wherein copper particles are formed in the channel of the metal copper pattern layer, and the channel of the metal copper pattern layer is a part of the semiconductor layer which is not covered by the metal copper pattern layer;
stripping the photoresist pattern layer by photoresist stripping liquid containing benzotriazole, wherein a passivation film is formed on the metal copper pattern layer and in a channel of the metal copper pattern layer in the stripping process, and the passivation film comprises a copper-benzotriazole complex;
cleaning the substrate with the photoresist pattern layer stripped by adopting a cleaning solution to remove the passivation film; wherein the cleaning solution comprises water, inorganic base, organic amine and a copper chelating agent; the pH value of the cleaning liquid is 10-11; the chelating ability of the copper chelating agent and copper is greater than that of benzotriazole and copper, and a water-soluble complex can be generated with copper; the organic amine is used for breaking coordination bonds in the copper-benzotriazole complex and dissolving benzotriazole.
5. The method of claim 4, wherein the copper chelating agent comprises disodium ethylenediaminetetraacetate, pentasodium diethylenetriaminepentaacetate, sodium iminodisuccinate salt or sodium diethyldithiocarbamate; the mass fraction of the copper chelating agent in the cleaning solution is 0.5-2%.
6. The method according to claim 4, wherein the organic amine is present in the cleaning solution in an amount of 2 to 8% by mass.
7. The method according to claim 4, wherein the organic amine comprises at least one of an alcohol amine, an amide, a short-chain aliphatic amine, an aromatic amine, and a nitrogen-containing heterocyclic substance; wherein, the alcohol amine substance comprises one or more of monoethanolamine, diethanolamine and triethanolamine; the amide substances comprise one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the nitrogen heterocyclic substance comprises one or more of piperidine, piperazine, imidazole, pyridine, piperidine and pyrrolidine; the aromatic amine comprises benzylamine; the short-chain aliphatic amine comprises one or more of monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1, 2-propylenediamine and hexamethylenediamine.
8. The method of claim 4, wherein the inorganic base comprises one or more of NaOH, KOH, and aqueous ammonia; the mass fraction of the inorganic base in the cleaning solution is 0.5-2%.
9. The method of claim 4, further comprising, after said cleaning with a cleaning solution:
and depositing a protective layer on the metal copper pattern layer and the area of the semiconductor layer which is not covered by the metal copper pattern layer.
10. The manufacturing method according to claim 4, further comprising, between the semiconductor layer and the substrate, sequentially stacking a gate electrode and a gate insulating layer provided on the substrate; the metal copper pattern layer includes a source electrode and a drain electrode disposed on the semiconductor layer in the same layer.
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CN101538710A (en) * 2009-04-30 2009-09-23 杭州百木表面技术有限公司 Method for continuously cleaning and passivating copper and copper alloy
CN105190846A (en) * 2013-04-10 2015-12-23 和光纯药工业株式会社 Cleaning agent for metal wiring substrate, and method for cleaning semiconductor substrate

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US7235188B2 (en) * 2002-10-22 2007-06-26 Ekc Technology, Inc. Aqueous phosphoric acid compositions for cleaning semiconductor devices

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CN101146901A (en) * 2005-01-27 2008-03-19 高级技术材料公司 Compositions for processing of semiconductor substrates
CN101538710A (en) * 2009-04-30 2009-09-23 杭州百木表面技术有限公司 Method for continuously cleaning and passivating copper and copper alloy
CN105190846A (en) * 2013-04-10 2015-12-23 和光纯药工业株式会社 Cleaning agent for metal wiring substrate, and method for cleaning semiconductor substrate

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