CN108573856A - A kind of preparation method and cleaning solution of array substrate - Google Patents
A kind of preparation method and cleaning solution of array substrate Download PDFInfo
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- CN108573856A CN108573856A CN201810333856.9A CN201810333856A CN108573856A CN 108573856 A CN108573856 A CN 108573856A CN 201810333856 A CN201810333856 A CN 201810333856A CN 108573856 A CN108573856 A CN 108573856A
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- copper
- amine
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- benzotriazole
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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
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- 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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
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- 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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
Abstract
The present invention provides a kind of cleaning solutions, the passivating film for including copper benzotriazole complex on washing array substrate, and the cleaning solution includes water, inorganic base, organic amine and copper chelator；The pH of the cleaning solution is 10~11；The sequestering power of the copper chelator and copper is more than the sequestering power of benzotriazole and copper, and can generate water soluble complex；The coordinate bond and dissolving benzotriazole that the organic amine is used to be broken in the copper benzotriazole complex.The cleaning solution is mainly used for being cleaned using the array substrate after the photoresist stripper stripping photoresist design layer containing benzotriazole.The present invention also provides application of the cleaning solution in array substrate preparation.
Description
Technical field
The present invention relates to display technology fields, and in particular to a kind of preparation method and cleaning solution of array substrate.
Background technology
Thin Film Transistor-LCD (Thin Film Transistor Liquid Crystal Display, referred to as
TFT-LCD) have the characteristics that small size, low power consumption, no radiation, occupy in the current flat panel display market predominantly
Position.As TFT-LCD is continued to develop, the requirement to resistance and electron mobility is higher and higher, higher to make TFT-LCD have
Contrast and image displaying quality, the low-resistance metallic copper of generally use is as making source-drain electrode, source electrode, grid line, number at present
According to the conductive material of the conductive patterns such as line.That is, copper wiring (then deposited metal Copper thin film is etched into required pattern again) is in TFT-
LCD is gradually in fashion in field.
Corrosion inhibitor of the generally use benzotriazole (BTA) as photoresist stripper in Cu processing procedures, BTA can inhale at present
It is attached to copper surface and forms one layer of passivating film containing conductive complex (copper-BTA), copper is risen in the stripping process of photoresist anti-
Erosion acts on.But removal more difficult copper-BTA, and its residual can cause large effect to the stability of display device, especially
When remaining Cu particles in the raceway groove (raceway groove between such as source-drain electrode) of conductive pattern on the substrate of display device, by Cu systems
After the photoresist stripper processing of journey, copper-BTA would also adhere on the Cu particles in raceway groove (as shown in Figure 1), greatly influence aobvious
Show the electrical of device.
Invention content
In consideration of it, the present invention provides a kind of passivation for cupric-benzotriazole complex on washing array substrate
The cleaning solution of film and the preparation method of array substrate, it is residual to avoid copper-BTA in the raceway groove of the conductive pattern of array substrate etc.
Substance is stayed to influence the quality of array substrate.
Specifically, the present invention provides a kind of preparation methods of array substrate, including：
One substrate is provided, semiconductor layer, metallic copper pattern layer and photoresist design layer are sequentially formed on one side in the substrate；
Dry etching, the metallic copper pattern layer are carried out to the semiconductor layer in the raceway groove of the metallic copper pattern layer
Raceway groove in formed copper particle；The raceway groove of the metallic copper pattern layer is that the semiconductor layer is not covered by the metallic copper pattern layer
The part of lid；
It is in the metallic copper pattern layer and golden using the photoresist stripper stripping photoresist design layer containing benzotriazole
Belong in the raceway groove of copper pattern layer and form passivating film in stripping process, the passivating film includes copper-benzotriazole complex；
Substrate after the stripping photoresist design layer is cleaned using cleaning solution, to remove the passivating film, is obtained
Array substrate；Wherein, the cleaning solution includes water, inorganic base, organic amine and copper chelator；The pH of the cleaning solution be 10~
11；The sequestering power of the copper chelator and copper is more than the sequestering power of benzotriazole and copper, and can be generated with copper water-soluble
Complex compound；The coordinate bond that the organic amine is used to be broken in the copper-benzotriazole complex, and dissolve benzotriazole.
Wherein, the copper chelator includes disodium ethylene diamine tetraacetate (EDTA- disodiums), diethylene triamine pentacetic acid (DTPA) sodium salt
In (five sodium of DTPA), iminodisuccinic acid sodium salt (tetra- sodium of IDS-) and sodium diethyldithiocarbamate (DDTC sodium salts)
It is one or more.
Wherein, the organic amine includes alcamines, amides, short-chain fat amine, aromatic amine, nitrogen heterocyclic ring substance.Into one
Step ground, the hydramine substance includes one or more in monoethanolamine, diethanol amine and triethanolamine；The amides object
Matter includes one in N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMA) and N-Methyl pyrrolidone (NMP)
Kind is a variety of；The nitrogen heterocyclic ring substance includes piperidines, piperazine, imidazoles, pyridine, hexahydropyridine, nafoxidine；The aromatic amine
Benzylamine etc. can be enumerated；The short-chain fat amine includes three kinds of methylamines (monomethyl amine, dimethylamine, trimethylamine), monoethyl amine, diethyls
Amine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1,2- propane diamine, hexamethylene diamine etc..
Wherein, the organic amine is n,N-Dimethylformamide, n,N-dimethylacetamide, triethanolamine and diethanol amine
In it is one or more.
Wherein, the inorganic base includes one or more in NaOH, KOH and ammonium hydroxide.
Wherein, in the cleaning solution, the mass fraction of copper chelator is 1-4%.
Wherein, in the cleaning solution, the mass fraction of organic amine is 2-8%.
Wherein, in the cleaning solution, the mass fraction of inorganic base is 0.5-2%.
Wherein, after the use cleaning solution is cleaned, further include：It described leads in the metallic copper pattern layer and partly
Body layer is not deposited protective layer on the region of metallic copper pattern layer covering.
Wherein, between the semiconductor layer and the substrate, further include the grid that is cascading on substrate and
Gate insulating layer；The metallic copper pattern layer includes the source electrode and drain electrode that same layer is arranged on the semiconductor layer.
Wherein, the semiconductor layer includes the first silicon fiml and the second silicon fiml set gradually over the substrate；Wherein, institute
It is non-crystalline silicon free from foreign meter to state the first silicon fiml；Second silicon fiml is the non-crystalline silicon of doped N-type impurity.
Wherein, second silicon fiml includes spaced source contact area and drain contact region, the source contact area
Under the source electrode, the drain contact region is located under the drain electrode.
In the preparation method of array substrate provided by the invention, using including water, inorganic base, organic amine and copper chelator
PH is clear to removing the progress of the array substrate after photoresist design layer using the photoresist stripper containing BTA for 10~11 cleaning solution
It washes, wherein inorganic base, organic amine and copper chelator are hydroaropic substance, and it is suitable that inorganic base and organic amine together provide
Alkaline environment, under the alkaline environment, the sequestering power of copper chelator and copper is more than the sequestering power of benzotriazole and copper, and
Water soluble complex can be generated；The organic amine is used to soften the coordination of passivating film, the fracture copper-benzotriazole complex
Key and dissolving benzotriazole.Therefore, which can preferably remove in the metallic copper pattern layer and metallic copper figure
The passivating film (including Cu particles, copper-BTA etc.) formed in photoresist stripping process in the raceway groove of pattern layer, and the cleaning solution will not
Structure in array substrate impacts, and will not especially make there is conductive residual between the raceway groove of metallic copper pattern layer
Object influences the electrical of subsequent array substrate.
The present invention also provides a kind of cleaning solutions, for including copper-benzotriazole complex on washing array substrate
Passivating film, the cleaning solution include water, inorganic base, organic amine and copper chelator；The pH of the cleaning solution is 10~11；The copper
The sequestering power of chelating agent and copper is more than the sequestering power of benzotriazole and copper, and can generate water soluble complex with copper；Institute
Coordinate bond of the organic amine for being broken in the copper-benzotriazole complex is stated, and dissolves benzotriazole.Wherein, this is clear
Various components in washing lotion are as described above.The cleaning solution is mainly used for removing photoresist pattern using the photoresist stripper containing BTA
Array substrate after layer is cleaned.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1 is the structural schematic diagram that the prior art removes front and back array substrate in copper wiring using photoresist stripper；
10 be substrate, 20 is semiconductor layer, 30 is initial copper film, and 30a is the metallic copper pattern layer after etching, and 40 be photoresist design layer,
30b is passivating film；
Fig. 2 is the flow chart of the preparation method of array substrate provided in an embodiment of the present invention；
Fig. 3 is structural schematic diagram of the substrate of (D) in Fig. 1 after step S03 cleanings；
Fig. 4 is that the substrate in one embodiment of the invention cleans the schematic diagram for re-forming protective layer later in step S03；
Fig. 5 is in another embodiment of the present invention by the board structure schematic diagram before and after dry etching in step S02；
Fig. 6 is the process of array substrate of the formation with gate patterns provided in another embodiment of the present invention.
Fig. 7 is the preparation process schematic diagram of array substrate in another embodiment of the present invention.
Specific implementation mode
Referring to Fig. 1, Fig. 1 is the knot that the prior art removes front and back array substrate in copper wiring using photoresist stripper
Structure schematic diagram.(B) etches initial copper film 30 and (such as is adopted with the photoresist design layer 40 of (A) in Fig. 1 for shade in Fig. 1
Use H2O2Carry out wet etching) after, metallic copper pattern layer 30 has been obtained, can be specifically source electrode, drain electrode.(C) is pair in Fig. 1
Semiconductor layer 20 in (B) substrate raceway groove carries out dry etching in Fig. 1, and semiconductor layer 20 is thinned, only leave can with source electrode,
Drain the region being in contact, and can be referred to as source contact area and drain contact region.It will be appreciated, however, that semiconductor layer
When 20 dry etching, since the etching gas used in dry etching can bombard metallic copper pattern layer 30 in etching process, this
Cu particles ((C) arrow is signified in such as Fig. 1) caused by sample bombardment will remain in half in the raceway groove of metallic copper pattern layer 30a
In conductor layer 20.
(D) is removed to photoresist design layer 40 using photoresist stripper in Fig. 1, leaves metallic copper pattern layer 30.It should
In step in conventionally used photoresist stripper contain benzotriazole (BTA), with prevent stripping photoresist 40 during copper quilt
Corrosion.Its etch-proof mechanism is substantially：BTA can be adsorbed on copper surface and form one layer of stable passivating film, the passivating film
Structure be Cu/Cu2O/Cu(Ⅰ)–BTA.Therefore, during removing photoresist, metallic copper pattern layer 30a and above-mentioned semiconductor layer
Remaining Cu particle surfaces can be capped one layer of passivating film 30b on 20.And Cu (I)-BTA in the passivating film relatively stablizes, it is difficult
It is dissolved in general organic solvent, and its is conductive.(D) circled passivating film in Fig. 1 is especially remained, because with conduction
Property, it can cause the conducting (being, for example, to be connected between adjacent source electrode, drain electrode) of metallic copper pattern layer 30, this will be greatly interfered with
Later stage is electrical using the display device made by the substrate, and then influences to show quality.
In view of the above problems, referring to Fig. 2, a kind of preparation side of array substrate provided in an embodiment of the present invention is described below
Method, including：
S01, a substrate 10 is provided, semiconductor layer 20, the metal being stacked is sequentially formed on one side in the substrate 10
Copper pattern layer 30a and photoresist design layer 40 (in such as Fig. 1 shown in (B))；
S02, dry etching is carried out to the semiconductor layer 20 in the raceway groove of the metallic copper pattern layer 30a (in such as Fig. 1
(C) shown in), the raceway groove of the metallic copper pattern layer 30a is interior to form copper particle；The raceway groove of metallic copper pattern layer 30a is semiconductor
Layer 20 is not by the part of metallic copper pattern layer 30a coverings；
S03, the photoresist design layer 40 is peeled off using the photoresist stripper containing benzotriazole；The metal copper pattern
Passivating film 30b (in such as Fig. 1 shown in (D)) is formed on layer 30a and in the raceway groove of metallic copper pattern layer 30a in stripping process, it is blunt
The material for changing film 30b includes Cu (I)-BTA conduction complexs；
S04, the substrate after the stripping photoresist design layer is cleaned using cleaning solution, to remove the passivating film,
Obtain array substrate；The cleaning solution includes：Water, inorganic base, organic amine and copper chelator；The pH of the cleaning solution is 10-11.
Step S01, the operation in S02 and S03 is substantially the same as described in Fig. 1.Some details are illustrated below.
In step S01, the material of substrate 1 is unlimited, can be glass substrate or flexible base board etc..In step S01, the gold
It is not that whole face is covered on semiconductor layer 20 to belong to copper pattern layer 30a, i.e. the layer of metallic copper pattern layer 30a and photoresist design layer 40
Stack structure is arranged at intervals on semiconductor layer 20.Here metallic copper pattern layer 30a may include source electrode, drain electrode, data line etc..
In step S02, the dry etching is not covered by the metallic copper pattern layer 30a to the semiconductor layer 20
Part come carry out.Here the purpose of dry etching is will to be in the semiconductor layer 20 between the raceway groove of the metallic copper pattern layer 30a
It is thinned, removes current-carrying part therein, only leave the conductive region that can be in contact with source electrode, drain electrode, source electrode can be referred to as and connect
Touch area and drain contact region.
As shown in figure 5, by the board structure signal before and after dry etching in step S02 in an embodiment of the present invention
Figure.Here metallic copper pattern layer 30a may particularly include copper source pole 31, copper drain electrode 32.Semiconductor layer 20 includes being successively set on
The first silicon fiml 21 on substrate 10 and the second silicon fiml 22；Wherein, the first silicon fiml 21 is non-crystalline silicon (a-Si) free from foreign meter, is used as
The channel of transistor；Second silicon fiml 22 is the non-crystalline silicon (N of doped N-type impurity+a-Si).By to metallic copper pattern layer 30a's
Semiconductor layer 20 between raceway groove etches, and eliminates the second silicon fiml 22 between copper source pole 31 and copper drain electrode 32, and is located at the raceway groove
The first interior silicon fiml 21 has also been thinned a bit, and thickness is about 0.05-0.1 μm.Semiconductor layer 20 after etching is first be thinned
Silicon fiml 21, and on 21 both ends of the first silicon fiml, respectively with source electrode, (source electrode connects the source contact area 221 that is in contact of drain electrode
Touch area), drain contact region 222.
Optionally, the etching gas that dry etching uses includes fluoro-gas and hydrogen.Further, the fluoro-gas
Including CF4、NF3And SF6At least one of.
In cleaning solution used in step S04, the sequestering power of the copper chelator and copper is more than the chela of benzotriazole and copper
Conjunction ability, and the copper chelator can generate water soluble complex with copper, convenient for being removed by washing., the organic amine is main
For softening the passivating film, the coordinate bond being broken in the copper-benzotriazole complex (copper-BTA), and make by the copper chela
The benzotriazole dissolving that mixture replaces.The organic amine also has certain alkalinity.Inorganic base is mainly used for providing alkalinity
Environment makes copper chelator, organic amine preferably play a role.
The inorganic base, organic amine and copper chelator are hydroaropic substance.Optionally, the copper chelator includes second two
Amine tetraacethyl disodium (EDTA- disodiums), diethylene triamine pentacetic acid (DTPA) sodium salt (five sodium of DTPA), iminodisuccinic acid sodium salt
It is one or more in (tetra- sodium of IDS-) and sodium diethyldithiocarbamate (DDTC sodium salts).
Optionally, the organic amine includes alcamines, amides, short-chain fat amine, aromatic amine, nitrogen heterocyclic ring substance.Into
One step, the hydramine substance includes one or more in monoethanolamine, diethanol amine and triethanolamine；The amides
Substance includes in N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMA) and N-Methyl pyrrolidone (NMP)
It is one or more；The nitrogen heterocyclic ring substance includes piperidines, piperazine, imidazoles, pyridine, hexahydropyridine, nafoxidine；The fragrance
Amine can enumerate benzylamine etc.；The short-chain fat amine includes three kinds of methylamines (monomethyl amine, dimethylamine, trimethylamine), monoethyl amine, diethyls
Amine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1,2- propane diamine, hexamethylene diamine etc..
It is further preferred that the organic amine be n,N-Dimethylformamide, n,N-dimethylacetamide, triethanolamine and
It is one or more in diethanol amine.
Optionally, the inorganic base includes one or more in NaOH, KOH and ammonium hydroxide.
Optionally, in the cleaning solution, the mass fraction of copper chelator 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 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 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.
Still optionally further, the cleaning solution is water, NaOH (1wt%), organic amine (5wt%), copper chelator (wt%)
Mixed solution, wherein the pH of the cleaning solution be 10.5, organic amine DMF, copper chelator be EDTA- disodiums.
Use the pH comprising water, inorganic base, organic amine and copper chelator be the above-mentioned cleaning solution of 10-11 to remove photoresist figure
Array substrate after pattern layer 40 is cleaned, and the structural schematic diagram of the substrate after cleaning is as shown in Figure 3.It is apparent that described in removal
The raceway groove of the passivating film 30b and metallic copper pattern layer 30a that are formed during removing photoresist on metallic copper pattern layer 30a it
Between the passivating film 20b (including Cu particles, copper-BTA etc.) that is formed during removing photoresist of semiconductor layer 20 preferably by
It removes, preferably reduces the surface roughness of substrate.
Optionally, after step S03 is cleaned using cleaning solution, which further includes：
S05, in the metallic copper pattern layer 30a and the semiconductor layer not by metallic copper pattern layer 30a coverings
Protective layer 50 is deposited on region, the structure of gained array substrate is as shown in Figure 4.The material of the protective layer 50 is insulation protection material
Material, for example, the silicon nitride (SiNx) of single layer either the silica (SiOx) of single layer or be silica (SiOx) and silicon nitride
(SiNx) lamination formed.Optionally, the thickness of protective layer 5 is
Protective layer 50 can be made by deposition and patterning process.Wherein, depositing operation includes chemical vapor deposition
(CVD), physical vapour deposition (PVD) (PVD) mode.Wherein CVD method includes but not limited to hot-wire chemical gas-phase deposition, plasma increasing
Extensive chemical is vapor-deposited (PECVD) etc..PVD method include but not limited to magnetron sputtering, vacuum evaporation, ion plating (such as electric arc from
Son plating, RF ion plating) etc..Preferably, protective film is formed using CVD modes.The patterning process is by complete material layer
In a part remove, to make this layer of remainder form the technology of required structure, generally include coating film forming, mask expose
Light, baking, development, etching, stripping and etc. in one or multi-step.
Optionally, in another embodiment of the present invention, the battle array before being cleaned using cleaning solution provided by the present application
Row substrate is bottom gate type, in Fig. 7 shown in (h), wherein between substrate 10 and semiconductor layer 20, further include：It stacks gradually and sets
Set grid 2 ' and gate insulating layer 3 ' on substrate 10.The above-mentioned metallic copper pattern layer referred to specifically includes same layer and sets herein
Set the source electrode 31 on semiconductor layer 20 and drain electrode 32.It is respectively provided with photoresist figure 41 to be stripped in source electrode 31 and drain electrode 32.
Here semiconductor layer 20 is with shown in (B) in above-mentioned Fig. 5, including the first silicon fiml 21, and on 21 both ends of the first silicon fiml
Source contact area 221, drain contact region 222.
Technical scheme of the present invention is illustrated with the preparation method of array substrate in Fig. 7 below.
S10, the array substrate for preparing (h) in Fig. 7, including：
S11, referring to Fig. 6, formed on substrate 10 using patterning processes include grid 2 ' figure；
S12, referring to (e) in Fig. 7, be sequentially depositing gate insulating layer on the substrate 1 for being formed with the gate patterns 2 '
(GI) 3 ' then, semiconductor layer 20, the second metallic copper film layer M2 use gray-level mask to form photoresist pattern 41；
S13, wet etching fall the second metallic copper film layer M2 on the outside of raceway groove, and are removed and dechannelled in the way of the ashing such as oxygen plasma
Interior photoresist (that is, thinnest part of photoresist pattern 41) forms (f) structure in Fig. 7；
S14, first dry ecthing are fallen to semiconductor layer 20, the GI layers 3 ' on the outside of raceway groove, and wet etching process is recycled to etch raceway groove
The second interior copper metal film M2 forms source electrode 31 and the drain electrode 32 of isolation, forms (g) structure in Fig. 7；
S15, through dry ecthing the etching to 20 layers of semiconductor in raceway groove is completed again, forms (h) structure in Fig. 7.
Wherein, step S11 specifically includes following steps：It is heavy using the method for sputtering or thermal evaporation on substrate referring to Fig. 6
Then the first metallic diaphragm M1 of product is coated with photoresist, using first of light shield by exposing, showing on the surface of the first metallic diaphragm M1
Shadow, photoetching and the selectively formed photoresist pattern 4 ' as shown in (b) in Fig. 6.Then using photoresist pattern 4 ' as shade to M1 into
Row etching, stripping photoresist, form grid and grid line graph etc..The step is similar to (A), (B), (D) in Fig. 1.And the grid formed
The figure and position of pole and grid line are same as the prior art, are in the viewing area (areas AA) of array substrate.And in array substrate
Metal film existing for non-display area can be still referred to as M1.
Wherein, in step S11, the figure of grid can also be the pattern layer that material is metallic copper.After removing photoresist,
The passivating film on 2 ' surface of grid can be removed come cleaning base plate with above-mentioned cleaning solution；Above-mentioned cleaning solution can not also be used to carry out
Cleaning, this not there's almost no copper particle, accordingly on substrate mainly before removing photoresist 4 ' by the region that grid 2 ' covers
Ground will not form passivating film in the region, almost not very likely influence the electrical of subsequent device.Further, cleaning solution used is
Water, NaOH (1wt%), organic amine (5wt%), the mixed solution of copper chelator (wt%), wherein the pH of the cleaning solution is
10.5, organic amine DMF, copper chelator are EDTA- disodiums.
In step S12, GI layers 3 ', semiconductor layer 2 can be deposited by chemical gas-phase method (CVD), the second metallic copper film layer
M2 can be deposited by physical vapour deposition (PVD) (PVD) and be obtained.The second metallic copper film layer M2 of (e) is equivalent in above-mentioned Fig. 1 in Fig. 7
30。
In Fig. 7 in the semiconductor layer 20 or Fig. 7 of (f) (g) be located at source electrode 31 and drain electrode 32 below semiconductor layer 20 include：
The first silicon fiml 21 and whole face that the whole face referred in Fig. 5 is covered on GI layers 3 ' are covered in the second silicon fiml of the first silicon fiml 21
22。
In step S14, when the second copper metal film M2 in wet etching raceway groove, H may be used2O2Come carry out.
In step S15, the etching gas that dry etching uses includes fluoro-gas and hydrogen.Further, described fluorine-containing
Gas includes CF4And SF6At least one of.
S20, the photoresist of (h) in Fig. 7 is removed using the photoresist stripper containing BTA, forms (i) structure (this in Fig. 7
In the passivating film that is formed in not specifically illustrated stripping process).
S30, the array substrate of (i) in Fig. 7 is cleaned using above-mentioned specific cleaning solution provided by the present application, obtains copper
Without the array substrate of passivating film on the film of material.
Cleaning solution used in step S30 can be water, NaOH (1wt%), organic amine (5wt%), copper chelator (wt%)
Mixed solution, wherein the pH of the cleaning solution is 10.5, organic amine DMF, and copper chelator is EDTA- disodiums.
By the cleaning of cleaning solution provided in an embodiment of the present invention, in array substrate, in metallic copper pattern layer and metal
Cupric-BTA the passivating films that (remaining Cu particles) is formed in photoresist stripping process in the raceway groove of copper pattern layer preferably by
It removes, and the structure that the cleaning solution will not be in array substrate impacts, and will not especially make the raceway groove of metallic copper pattern layer
Between there is conductive residue, influence the electrical of subsequent array substrate, while also preferably reducing the rough surface of substrate
Degree.Certainly, cleaning solution provided by the invention is also not necessarily limited to above application, if in array substrate, metallic copper pattern layer (including
Grid, grid line (scan line), source electrode, drain electrode, data line etc.) on photoresist figure using the photoresist stripper containing BTA into
After row stripping, cleaning solution provided by the invention may be used to start the cleaning processing, efficiently remove passivating film.To be cleaned
The region of array substrate is not limited to its visible area (areas AA, the left side of (i) in Fig. 7), may also include the non-areas AA (in Fig. 7 (i)
The rightmost side).
Only several embodiments of the present invention are expressed for above example, the description thereof is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
It encloses.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of cleaning solution, for the passivating film on washing array substrate, the passivating film includes copper-benzotriazole cooperation
Object, which is characterized in that the cleaning solution includes water, inorganic base, organic amine and copper chelator；The pH of the cleaning solution be 10~
11；The sequestering power of the copper chelator and copper is more than the sequestering power of benzotriazole and copper, and can be generated with copper water-soluble
Complex compound；The coordinate bond that the organic amine is used to be broken in the copper-benzotriazole complex, and dissolve benzotriazole.
2. cleaning solution as described in claim 1, which is characterized in that in the cleaning solution, the mass fraction of copper chelator is 1-
4%；The mass fraction of organic amine is 2-8%, and the mass fraction of inorganic base is 0.5-2%.
3. cleaning solution as described in claim 1, which is characterized in that the copper chelator includes disodium ethylene diamine tetraacetate, two
Ethylene Pentetate Pentasodium, iminodisuccinic acid sodium salt or sodium diethyldithiocarbamate；
The inorganic base includes one or more in NaOH, KOH and ammonium hydroxide；
The organic amine includes at least one of alcamines, amides, short-chain fat amine, aromatic amine and nitrogen heterocyclic ring substance；
Wherein, the hydramine substance includes one or more in monoethanolamine, diethanol amine and triethanolamine；The amides object
Matter includes one or more in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone；It is described to contain
Azacyclo- substance includes one or more in piperidines, piperazine, imidazoles, pyridine, hexahydropyridine and nafoxidine；The aromatic amine
Including benzylamine；The short-chain fat amine includes monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, n-propylamine, isopropylamine,
It is one or more in diisopropylamine, n-butylamine, ethylenediamine, 1,2- propane diamine and hexamethylene diamine.
4. a kind of preparation method of array substrate, which is characterized in that including：
One substrate is provided, semiconductor layer, metallic copper pattern layer and photoresist design layer are sequentially formed on one side in the substrate；
Dry etching, the ditch of the metallic copper pattern layer are carried out to the semiconductor layer in the raceway groove of the metallic copper pattern layer
Copper particle is formed in road, the raceway groove of the metallic copper pattern layer is that the semiconductor layer is not covered by the metallic copper pattern layer
Part；
The photoresist design layer is removed using the photoresist stripper containing benzotriazole, in the metallic copper pattern layer and metallic copper
Passivating film is formed in stripping process in the raceway groove of pattern layer, the passivating film includes copper-benzotriazole complex；
Substrate after the stripping photoresist design layer is cleaned using cleaning solution, to remove the passivating film；Wherein, described
Cleaning solution includes water, inorganic base, organic amine and copper chelator；The pH of the cleaning solution is 10~11；The copper chelator and copper
Sequestering power be more than benzotriazole and copper sequestering power, and can with copper generate water soluble complex；The organic amine is used
In the coordinate bond being broken in the copper-benzotriazole complex, and dissolve benzotriazole.
5. preparation method as claimed in claim 4, which is characterized in that the copper chelator include disodium ethylene diamine tetraacetate,
Five sodium of diethylene triamine pentacetic acid (DTPA), iminodisuccinic acid sodium salt or sodium diethyldithiocarbamate；The copper chelator
Mass fraction in cleaning solution is 0.5-2%.
6. preparation method as claimed in claim 4, which is characterized in that mass fraction of the organic amine in cleaning solution is 2-
8%.
7. preparation method as claimed in claim 4, which is characterized in that the organic amine includes alcamines, amides, short chain fat
At least one of fat amine, aromatic amine and nitrogen heterocyclic ring substance；Wherein, the hydramine substance includes monoethanolamine, diethanol
It is one or more in amine and triethanolamine；The amide substance includes N,N-dimethylformamide, N, N- dimethylacetamides
It is one or more in amine and N-Methyl pyrrolidone；The nitrogen heterocyclic ring substance includes piperidines, piperazine, imidazoles, pyridine, hexahydro
It is one or more in pyridine and nafoxidine；The aromatic amine includes benzylamine；The short-chain fat amine includes monomethyl amine, diformazan
Amine, trimethylamine, monoethyl amine, diethylamine, n-propylamine, isopropylamine, diisopropylamine, n-butylamine, ethylenediamine, 1,2- propane diamine and oneself two
It is one or more in amine.
8. preparation method as claimed in claim 4, which is characterized in that the inorganic base includes one in NaOH, KOH and ammonium hydroxide
Kind is a variety of；Mass fraction of the inorganic base in cleaning solution is 0.5-2%.
9. preparation method as claimed in claim 4, which is characterized in that after the use cleaning solution is cleaned, also wrap
It includes：
It is not protected by deposition on the region of metallic copper pattern layer covering in the metallic copper pattern layer and the semiconductor layer
Layer.
10. preparation method as claimed in claim 4, which is characterized in that between the semiconductor layer and the substrate, also wrap
Include the grid and gate insulating layer being cascading on substrate；The metallic copper pattern layer includes same layer setting described half
Source electrode and drain electrode in conductor layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040137736A1 (en) * | 2002-10-22 | 2004-07-15 | Jerome Daviot | Aqueous phosphoric acid compositions for cleaning semiconductor devices |
| 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 |
-
2018
- 2018-04-13 CN CN201810333856.9A patent/CN108573856B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040137736A1 (en) * | 2002-10-22 | 2004-07-15 | Jerome Daviot | Aqueous phosphoric acid compositions for cleaning semiconductor devices |
| 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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