CN101098989A - Copper etchant and method of etching - Google Patents
Copper etchant and method of etching Download PDFInfo
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- CN101098989A CN101098989A CNA200580046553XA CN200580046553A CN101098989A CN 101098989 A CN101098989 A CN 101098989A CN A200580046553X A CNA200580046553X A CN A200580046553XA CN 200580046553 A CN200580046553 A CN 200580046553A CN 101098989 A CN101098989 A CN 101098989A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
Abstract
The present invention provides copper etchant and a method of etching which can perform selective uniform etching of copper or a copper alloy even when mixed with another metal. The copper etchant at least contains ammonium oxalate, hydrogen peroxide and a surfactant, and has a surface tension less than 45mN/m and PH from 6.0 to 8.5. The ammonium oxalate functions as a complex agent for dissolving copper in the form of a copper complex. The hydrogen peroxide functions as an oxidant for oxidizing a copper surface. The addition of the surfactant lowers the surface tension of the etchant below 45 mN/m. As a result, substrate surface wetting and etchant permeation into high-aspect portions of a substrate structure can be enhanced, and in the co-presence of a metal with high conductivity for wiring or electrode, copper or copper alloys can be etched uniformly and selectively.
Description
Technical field
The present invention relates to select copper or copper alloy carries out etching solution for etching and use this etching solution that copper or copper alloy are carried out etching method by wet etch method.Specifically, the present invention relates in the manufacturing of semiconductor devicess such as semiconductor device, liquid crystal indicator, printed base plate, IC-card etc., be suitable for the etching solution and the engraving method of the copper of etch copper or copper alloy thin films etc.
Background technology
Semiconductor devices such as semiconductor device, liquid crystal indicator, printed base plate, IC-card etc. constitute metallic film element or electrode wiring members etc. with formation patterns such as metallic films during fabrication usually on substrate.
Processing technology as the pattern that this metallic film is formed fine structure such as distribution, can enumerate: as mask, utilize chemical reagent to carry out etching and the wet etch method that carries out pattern processing with the photoresist material pattern that on the metallic film surface, forms by photoetching technique; With dry ecthing methods such as ion etching or plasma etchings.
Wherein, compare with dry ecthing method, wet etch method need not the high price device, use be the lower reagent of price, so it is favourable at economic aspect.In addition, wet etch method also has following advantage: even the area of substrate is big and the production efficiency (promptly increasing the number of treatment substrate) of raising time per unit, wet etch method also can carry out uniform etching, and be not subject to the influence of etch target shape, can be used in etch target with three-dimensional structure.Therefore, now manufacture method that adopt wet etch method as Thinfilm pattern more.
In recent years, along with the raising of the degree that becomes more meticulous of processing graphic pattern, postpone, be difficult for aspect the physical properties such as broken string the requirement of the material of the metallic film element that is used for semi-conductor and liquid crystal indicator etc. and uses such as electrode distribution, other elements also more and more higher at no distribution.Under this situation, material as such element etc., the material of each excellent such as the processibility when expecting that a kind of resistance value is low and making Thinfilm pattern is good, and copper or copper alloy have been subjected to attention as such material, its use is increasing recently always.
In the past, as etching solution used when the element that uses copper or copper alloy etc. forms pattern, use alkaline etching liquid such as amine or ammoniacal liquor or ferric chloride in aqueous solution, copper chloride solution, the persulphate aqueous solution usually, mix the acidic etching liquid that obtains (for example patent documentation 1～5 etc.) by sulfuric acid and hydrogen peroxide.
When using these etching solutions to make copper or copper alloy element form pattern by wet etch method, not only the etching to copper or copper alloy is even to require etching solution, also requires to have the selection etching to copper or copper alloy.Promptly, when the element of copper or copper alloy had been used in making, metallic film lamination copper or copper alloy on the insulativity substrate that is for example formed by organism such as silicon, glass, aluminum oxide or macromolecule resins beyond copper such as nickel or nickelalloy or copper alloy formed stack membrane.Sometimes, from this stack membrane only etching remove copper or copper alloy thin films, imbed other metals in the part of having removed copper or copper alloy thin films, make element etc., perhaps, only select etch copper or copper alloy thin films as the base metal that forms solder joint.In this case, etching solution must can be only optionally and equably etch copper or copper alloy, other metals of not etching.
Patent documentation 1: the spy opens the 2002-266087 communique
Patent documentation 2: the spy opens flat 10-96088 communique
Patent documentation 3: the spy opens flat 8-60386 communique
Patent documentation 4: the spy opens the 2002-348685 communique
Patent documentation 5: the spy opens the 2000-248386 communique
Summary of the invention
But, the normal etch liquid of using in the past copper or copper alloy, for example for the acidic etching liquid that contains acid such as sulfuric acid and aqueous hydrogen peroxide solution etc., copper or copper alloy are than the etching that is easier to be subjected to these etching solutions, but because these etching solutions are main component with water, so insufficient to the wettability of copper or copper alloy.Therefore, in retrofit, be easy to generate etching delay or etch residue.In addition, for existing etching solution, with the coexistence system of other metals in, existing etching solution to other not etchings of metal and the only etching selectivity of etch copper or copper alloy is low.Owing to this reason, when using copper or copper alloy to form meticulous element etc., be difficult to selectively and etch copper or copper alloy equably.
The objective of the invention is to solve above-mentioned problem in the past, though provide under a kind of situation that other metals are arranged in coexistence also can be selectively and equably the copper of etch copper or copper alloy or copper alloy with etching solution with use the method for this etching solution etch copper or copper alloy.
The etching solution of copper of the present invention is the etching solution that is used for etch copper or copper alloy, it is characterized in that, contains ammonium oxalate, hydrogen peroxide and tensio-active agent at least, and surface tension is below the 45mN/m, and pH is 6.0～8.5.
Promptly, for solving above-mentioned problem, the present inventor specializes in, found that, even other metals with superior electrical conductivity (aluminium is particularly arranged in coexistence, titanium, nickel, tin, plumbous, silver, gold, palladium, or be the alloy of main composition with more than one these metals) the situation of meticulous device structure under, containing ammonium oxalate and hydrogen peroxide and contain the etching solution of specific pH that the surface tension that enough makes etching solution is reduced to the tensio-active agent of the following amount of 45mN/m also can be selectively and an etch copper or copper alloy equably, thereby has finished the present invention.
The etching solution of copper of the present invention preferably also contains the amino acid of 0.2 weight %～25 weight %, the preferred glycine of this amino acid.
Among the present invention, as tensio-active agent, suitable having has and is selected from by-SO
3The M base ,-OSO
3M base and-the COOM base (wherein, M represents basic metal dvielement or hydrogen atom) in the group formed one or more functional group aniorfic surfactant and/or have the nonionic surface active agent of the repeat unit structure of oxyalkylene, preferred especially polyoxyalkylene alkyl derivative.
The content of each composition in the preferred etching solution of the present invention is as described below: ammonium oxalate 0.05 weight %～5 weight %, hydrogen peroxidase 10 .2 weight %～10 weight %, tensio-active agent 0.0001 weight %～5 weight %.
Utilize the etching solution of copper of the present invention, under can particularly being selected from by aluminium, titanium, nickel, tin, lead, silver, gold, palladium or the coexistence of these metals at the metal that distribution or electrode are used with superior electrical conductivity as the metal in the group of the alloy composition of main composition with more than one, evenly and selectively etch copper or copper alloy.This etching solution preferably uses 20 ℃～50 ℃ temperature.
The etching solution of copper of the present invention is preferably as follows and is prepared: in the time of will containing the effective constituent of ammonium oxalate, hydrogen peroxide and tensio-active agent and water at least and mix the etching solution for preparing copper, effective constituent that will be except hydrogen peroxide is with after water mixes, in this mixture, add and the mixing hydrogen peroxide, prepare the etching solution of copper of the present invention thus.
Engraving method of the present invention is the method for selective etch copper or copper alloy under the coexistence of the metal with superior electrical conductivity that distribution or electrode are used, it is characterized in that, use the etching solution of the invention described above, engraving method of the present invention can be evenly and etch copper or copper alloy selectively.
Etching solution and engraving method according to copper of the present invention, substrate for the rhythmo structure of the metal that has copper or copper alloy and other good conductivity in the electrode of the thin film transistor of semiconductor device or liquid crystal indicator or manufacturing of distribution or salient point etc., can carry out optionally uniform etching to copper or copper alloy, do not have residue at meticulous position, and can not corrode the electronic unit on the substrate, various stack membranes etc.Therefore, compare, can realize the optionally high precision etching that size control is higher, improve the electrical characteristic and the service performance of equipment, can seek to improve the performance of various devices such as semiconductor element thus with existing method.
Embodiment
Describe the etching solution of copper of the present invention and the embodiment of engraving method below in detail.
The etch target of the etching solution of copper of the present invention is not limited to fine copper, can be copper alloy.As copper alloy, copper content is to be suitable more than the 50 weight %, and the metal of alloying in the copper alloy is not particularly limited, and can enumerate in for example tin, lead, zinc, nickel, the manganese etc. one or more.
The etching solution of copper of the present invention is prepared with the form of the aqueous solution that contains ammonium oxalate, hydrogen peroxide and tensio-active agent and water usually, and this aqueous solution also contains amino acid sometimes.
Ammonium oxalate is as forming copper complex so that the complexing agent of copper dissolution plays a role with copper, and its concentration in etching solution is preferably 0.05 weight %～5 weight %, particularly 1.5 weight %～4 weight %.
The concentration of ammonium oxalate is crossed when low, and is inhomogeneous to the etching of copper sometimes, and used time of etching is long.On the contrary, if the excessive concentration of ammonium oxalate, then because the solubleness of ammonium oxalate separating out of ammonium oxalate occur and might wait in etching system.
Hydrogen peroxide plays a role as the oxygenant that the copper surface is carried out oxidation, and its concentration is preferably 0.2 weight %～10 weight %, particularly 0.5 weight %～5 weight %.The concentration of hydrogen peroxide is crossed when hanging down, and the time that the etching of copper sometimes needs is long.On the contrary, if the excessive concentration of hydrogen peroxide then during hydrogen peroxide decomposition, the rapid heating of etching solution may occur or produce a large amount of situations such as oxygen, there is the problem of security aspect.Therefore, when preparing the etching solution of copper of the present invention, preferably with other effective constituents with after water mixes, add hydrogen peroxide at last.
About the concentration of ammonium oxalate in the etching solution and hydrogen peroxide, only need in above-mentioned scope, to adjust suitably to determine that according to the etching speed of necessity the concentration of etching solution mesoxalic acid ammonium and hydrogen peroxide gets final product.
Etching solution for copper of the present invention, by making it contain tensio-active agent, the surface tension of etching solution is dropped to below the 45mN/m, improve the wettability and raising etching solution infiltration in board structure high-order portion of etching solution thus, can make etching more even real estate.As tensio-active agent, can enumerate aniorfic surfactant, cationic surfactant, amphoterics and nonionic surface active agent.Wherein, preferred anionic type tensio-active agent, amphoterics and nonionic surface active agent, special preferred anionic type tensio-active agent and nonionic surface active agent.These tensio-active agents can use separately, but also appropriate combination is used inhomogeneous two or more tensio-active agent.Wherein, the infiltration that is combined in chemical etchant of aniorfic surfactant and nonionic surface active agent carries high and low bubble, pollutes that to remove the effect aspect be preferred.
As nonionic surface active agent, carboxylic acid type, sulfonic acid type, sulfuric acid ester type, phosphate type etc. can be enumerated,, amino acid pattern, betaine type etc. can be enumerated as amphoterics, as nonionic surface active agent, can enumerate polyethylene glycol type, polyvalent alcohol type etc.
In the aniorfic surfactant, preferred sulfonic acid type (has-SO
3 -The tensio-active agent of base), sulfuric acid ester type (has-OSO
3 -The base tensio-active agent) and carboxylic acid type (have-COO
-The tensio-active agent of base).Specifically, preferably have-SO
3The M base ,-OSO
3The M base ,-compound of at least one group in the COOM base (wherein, M is basic metal dvielement or hydrogen atom).More particularly, preferably use alkylsulphonic acid, alkyl benzene sulphonate (ABS), alkyl sulfuric ester class, alkyl ether sulphate class, alkyl carboxylic acid and these salt.
In the nonionic surface active agent,, can enumerate polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, Vykamol Sorbitol 8B etc. as polyethylene glycol type.In addition, as polyalkylene glycol type, can enumerate polyoxyethylene poly-oxygen propylene aether, polyoxyethylene polyoxy butylene ether, polyoxyethylene polyoxy-propylene etc.As the polyvalent alcohol type, can enumerate glycerin fatty acid ester, sorbitan esters of fatty acids etc.From the angle of chemical stability, removing property of pollution excellence and low whipability excellence, preferred polyoxyalkylene (alkyl) ether etc. that uses in these nonionic surface active agent.
As long as it is that 45mN/m is following that tensio-active agent adds the surface tension of the etching solution that becomes to make copper, the concentration of tensio-active agent in the etching solution of copper is not particularly limited, but the surfactant concentrations in the etching solution of copper of the present invention is preferably 0.0001 weight %～5 weight %, particularly 0.001 weight %～1 weight %.Surfactant concentrations is crossed when hanging down, the infiltration of the raising etching solution that brings by tensio-active agent and to remove the performance of various particle contaminations insufficient, and surfactant concentrations is when too high, it is obvious that foaming becomes, in some engraving method, become improper, and the load when disposing waste liquid sometimes increases.
The surface tension that is characterized as of the etching solution of copper of the present invention is below the 45mN/m, because surface tension is so little, so can guarantee sufficient wettability.
In addition, the etching solution of copper of the present invention can also further contain amino acid such as glycine.As adding the effect that amino acid brings, except pH shock absorption described later, can also enumerate and reduce as the influence of the concentration of the hydrogen peroxide of oxygenant to etching speed.Promptly, hydrogen peroxide is through decomposing inevitably after a while, but in being added with amino acid whose system, etching speed not too is subjected to the influence of concentration of hydrogen peroxide, thus can avoid hydrogen peroxide in time passing and the rapid decline of decomposing caused etching speed.In addition, in not adding amino acid whose system, etching speed is determined by unsettled concentration of hydrogen peroxide, the problem that has etching speed stability aspect, and be added with in the amino acid whose system, the influence of concentration of hydrogen peroxide is little, so can etching speed be adjusted into stable arbitrary speed by adjusting etchant concentration.In this case, amino acid whose content is preferably set to 0.2 weight %～25 weight %, particularly 1 weight %～15 weight % in the etching solution of copper.
The pH of the etching solution of copper of the present invention is 6.0～8.5, is preferably 6.5～8.Compare with this scope, the pH of the etching solution of copper crosses when hanging down or when too high, the etching selectivity with the coexistence metal is low sometimes.As required, can use acid, alkali composition to adjust the pH of the etching solution of copper.As employed sour composition, can enumerate organic acid and mineral acids such as hydrochloric acid, nitric acid such as acetate, especially preferably use oxalic acid aqueous solution.On the other hand,, can use ammoniacal liquor or sodium hydroxide, potassium hydroxide aqueous solution etc., especially preferably use ammoniacal liquor as the alkali composition.
Preferably not only when the preparation copper etchant solution, carry out the adjustment of the pH of copper etchant solution, in etching, also carry out the adjustment of the pH of copper etchant solution.That is, carry out along with etched, the pH change, but pH is when breaking away from preferred range, and with respect to the coexistence metal, the etching selectivity of copper reduces.In addition also because, too high when particularly the pH of the etching solution of copper increases as the decomposition rate of the hydrogen peroxide of oxygenant, the lifetime of the etching solution of copper consequently.In addition, when the etching solution of copper of the present invention contained amino acid, because amino acid whose pH shock absorption, the amplitude of fluctuation of pH was little, need not frequently to carry out the adjustment of pH, is very favorable so contain amino acid.
When using the etching solution of this copper of the present invention to carry out etching,, then, might hinder uniform etching particularly along with the becoming more meticulous of the pattern dimension that carries out etching and processing if there are insoluble impuritiess such as particulate in the etching solution.Therefore, preferably remove insoluble impuritiess such as particulate in the etching solution by the method that copper etchant solution is filtered etc. copper etchant solution by accurate filter.Filter type can be a through type, but removes the angle of efficient from particulate, and is more preferably circulating.As for the aperture of accurate filter, suitably select to get final product, the aperture of accurate filter is below the 0.2 μ m usually, is preferably especially below the 0.1 μ m.
As for the material of strainer, as long as chemical property-physical properties is stable to filtering etching solution, can be any material, for example can enumerate fluorine resin such as high density polyethylene(HDPE), tetrafluoroethylene class material etc.The etching solution of copper is preferably removed insoluble impuritiess such as particulate through such filtration treatment so that for example the above particulate of diameter 0.5 μ m be 1000/below the ml.
Using the etching solution of copper of the present invention to carry out etching method can implement in about 15 ℃～30 ℃ room temperature, but in order to improve etching speed, also can heat etching solution.Usually, the temperature of etching solution is 10 ℃～60 ℃, is preferably 20 ℃～50 ℃ especially.
On by the insulativity substrate that for example organism such as silicon, glass, aluminum oxide or macromolecule resin form, when forming aluminium, nickel, tin, lead, silver, gold, palladium or with more than one these metals being the metallic membrane of excellent electric conductivity of alloy etc. of main composition, engraving method of the present invention can be applied to be stacked in the copper on this metallic membrane or the etching of copper alloy thin films.
Using the engraving method of the present invention of copper etchant solution of the present invention is arbitrarily, can use existing known machine, the device that is used for wet etching to carry out.
For example,, can enumerate and in etching bath, fill etching solution, etch target is dipped in immersion process wherein etc. as the contact method of etch target and etching solution.At this moment, this etch target is shaken, or force to make the etching solution circulation in the groove, so can carry out etching more equably.In addition, can enumerate spray pattern that etching solution is sprayed to the face of etch target or by nozzle to the rotation mode of the etch target ejection etching solution of rotation etc.The also preferred and immersion way of these treatment processs is used in combination.
In the engraving method of the present invention, preferably remove copper or copper alloy thin films by being etched with dissolving, carry out the suitableeest etching (just etching) until the metallic film of the lower floor of copper or copper alloy thin films or terminal point that substrate exposes with after the suitableeest etching, further carry out the etched etching (over etching) of crossing.In this case, be not particularly limited, but be preferably 5%～200% of the suitableeest etching period, be preferably 10%～100% of the suitableeest etching period especially crossing etching period.
Embodiment
Enumerate embodiment and comparative example below, be described more specifically the present invention, but only otherwise exceed aim of the present invention, the present invention is not limited to following embodiment.
In addition, hereinafter the surface tension of etching solution uses tensiometer (the CBVP SURFACE TENSIONMETER A3 that consonance science (strain) is produced) to measure.In addition, pH uses pH meter ((strain) hole field makes the D-24 that is produced) to measure.
Embodiment 1
Copper (Cu), silver (Ag), nickel (Ni), tin (Sn), tin/silver (96.5 weight %/3.5 weight %) alloy (Sn-Ag), aluminium (Al) plate with thick 0.5mm cuts into wide 10mm * long 10mm respectively, as dissolving metal speed evaluation test film.
Get 100g is added with 3 weight % in water ammonium oxalate, the hydrogen peroxide of 0.5 weight % and the tensio-active agent (alkyl of oxyalkylene condenses (carbonatoms the is 12) ether of 0.005 weight %, Sanyo changes into the NL110 that industry (strain) is produced) etching solution, pack into the beaker of 100ml is adjusted into 25 ℃ with the temperature of etching solution.The surface tension and the pH of this etching solution are as shown in table 1.
Each test film was soaked 2 hours in this etching solution, calculate the dissolution rate of each metal according to the weight difference before and after soaking.In addition, calculate etching speed than (dissolution rate of the dissolution rate of copper/each metal), with this as etching selectivity to copper.These the results are shown in Table 1.
Comparative example 1
As embodiment 1, wherein in etching solution, do not add tensio-active agent, in addition, prepare etching solution similarly to Example 1, and similarly measure surface tension and pH, carry out the test of dissolving metal speed evaluation simultaneously, the results are shown in Table 1.
Table 1
| Example | Etching solution | Metal species | Dissolution rate (milligram/hour) | Etching selectivity (-) | ||||
| Form (weight %) | Surface tension (mN/m) | pH | ||||||
| Ammonium oxalate | Hydrogen peroxide | Tensio-active agent | ||||||
| Embodiment 1 | 3 | 0.5 | 0.005 | 37 | 6.55 | Cu | 5.49 | 1 |
| Ag | 0.1 | 55 | ||||||
| Ni | 0.02 | 275 | ||||||
| Sn | 0.02 | 275 | ||||||
| Sn-Ag | 0.05 | 100 | ||||||
| Al | -0.02 | - | ||||||
| Comparative example 1 | 3 | 0.5 | 0 | 60 | 6.53 | Cu | 5.31 | 1 |
| Ag | 0.07 | 76 | ||||||
| Ni | 0.07 | 76 | ||||||
| Sn | 0.01 | 531 | ||||||
| Sn-Ag | 0.2 | 27 | ||||||
| Al | -0.03 | - | ||||||
As known from Table 1, etching solution of the present invention has big selectivity to silver (Ag), nickel (Ni), tin (Sn), tin/silver (96.5 weight %/3.5 weight %) alloy (Sn-Ag), aluminium (Al), can not corrode these metals, optionally etch copper.In addition, the dissolution rate to copper among comparative example 1 and the embodiment 1 equates substantially, thereby as can be known, adds tensio-active agent in the etching solution to the not influence of dissolution rate of copper.
Embodiment 2
In order to estimate the etching characteristic of copper, make following substrate (all standing substrate), wherein, have the heat oxide film (SiO of thick 10nm
2) 4 inches silicon (Si) substrate on pile up by sputtering method that thickness is arranged is the titanium (Ti) of 100nm, at this Ti/SiO
2Further pile up on/Si the substrate that thickness is arranged is the copper (Cu) of 300nm.Spin coating eurymeric photoresist material resin on this all standing substrate (the about 1 μ m of thickness) forms pattern by photoetching technique with it then, makes the line of existence 5 μ m～100 μ m and the substrate (patterned substrate) of pattern at interval.Should patterned substrate cut into and be about 50mm * wide about 10mm, make to estimate and use sample.
Form at the etching solution identical, under the etching solution temperature, under this sample is rocked up and down, carry out etching in etching solution with embodiment 1.
The suitableeest etching period for when etching begins to time of terminal point.Terminal point is determined by the time point that the dissolving metal of answering etched part on the visual observation substrate exposes substrate.In addition, suitably calculate the mistake etching period of determining regulation according to the suitableeest etching period and overetched etch quantity (crossing etch quantity).
After the end of etching excessively of specified time, take out sample, after 1 minute, carry out air-dry with clean air with the pure water cleaning.
After the etching, carry out the observation of substrate surface with laser microscope (VK-8500 that キ one ェ Application ス society produces) and scanning electron microscope (6320F that NEC society produces), research has or not etch residue, the results are shown in Table 2.
Comparative example 2
As embodiment 2, wherein, except make form with the same etching solution of comparative example 1, carry out the evaluation of etching characteristic similarly to Example 2, the results are shown in Table 2.
Table 2
| Example | The suitableeest etching period (second) | Have or not the copper residue after the etching | |||
| Cross etch quantity (all etching periods) | |||||
| 0% (25 seconds) | 50% (38 seconds) | 100% (50 seconds) | 150% (63 seconds) | ||
| Embodiment 2 | 25 | Have | Do not have | Do not have | Do not have |
| Comparative example 2 | 25 | Have | Have | Have | Do not have |
As shown in Table 2, etching solution of the present invention can be with the less uniform etching that etch quantity carries out meticulous no residue of crossing to the infiltration excellence of fine pattern.
Embodiment 3
Get 100g is added with 3 weight % in water ammonium oxalate, the glycine of 5 weight %, the hydrogen peroxide of 0.5 weight % and the tensio-active agent (alkyl of oxyalkylene condenses (carbonatoms the is 12) ether of 0.005 weight %, Sanyo changes into the NL110 that industry (strain) is produced) etching solution, pack into the beaker of 100ml is adjusted into 28 ℃ with the temperature of etching solution.The surface tension of this etching solution and pH are shown in table 3-1.
Use this etching solution, the evaluation of etching characteristic is carried out in operation similarly to Example 2, the results are shown in Table 3-2.
Comparative example 3
As embodiment 1, wherein, do not add tensio-active agent, in addition, prepare etching solution similarly to Example 1.The surface tension of this etching solution and pH are shown in table 3-1.
Use this etching solution, the evaluation of etching characteristic is carried out in operation similarly to Example 2, the results are shown in Table 3-2.
Table 3
Table 3-1
| Example | Etching solution | |||||
| Form (weight %) | Surface tension (mN/m) | pH | ||||
| Ammonium oxalate | Glycine | Hydrogen peroxide | Tensio-active agent | |||
| Embodiment 3 | 3 | 5 | 0.5 | 0.005 | 34 | 6.36 |
| Comparative example 3 | 3 | 5 | 0.5 | 0 | 63 | 6.35 |
Table 3-2
| Example | The suitableeest etching period (second) | Have or not the copper residue after the etching | |||
| Cross etch quantity (all etching periods) | |||||
| 0% (18 seconds) | 50% (27 seconds) | 100% (36 seconds) | 150% (45 seconds) | ||
| Embodiment 3 | 18 | Have | Do not have | Do not have | Do not have |
| Comparative example 3 | 18 | Have | Have | Have | Do not have |
As shown in Table 3, etching solution of the present invention can be with the less uniform etching that etch quantity carries out meticulous no residue of crossing to the infiltration excellence of fine pattern.
Utilizability on the industry
The etching solution of copper of the present invention and engraving method are to the usefulness that is formed with of the copper in the manufacturing of the semiconductor equipments such as semiconductor device, liquid crystal indicator, printed base plate, IC-card etc. or copper alloy thin films element or electrode wiring member etc.
Claims (19)
1, a kind of etching solution of copper, it is the etching solution that is used for etch copper or copper alloy, it is characterized in that, and described etching solution contains ammonium oxalate, hydrogen peroxide and tensio-active agent at least, and the surface tension of this etching solution is below the 45mN/m, and pH is 6.0～8.5.
2, the etching solution of copper as claimed in claim 1 is characterized in that, the etching solution of described copper also contains amino acid, and amino acid whose content is 0.2 weight %～25 weight %.
3, the etching solution of copper as claimed in claim 2 is characterized in that, described amino acid is glycine.
4, the etching solution of copper as claimed in claim 1 is characterized in that, described tensio-active agent is to have to be selected from by-SO
3The M base ,-OSO
3M base and-in the group that the COOM base is formed one or more functional group aniorfic surfactant and/or have the nonionic surface active agent of the repeat unit structure of oxyalkylene, wherein, M represents alkali metal or hydrogen atom.
5, the etching solution of copper as claimed in claim 4 is characterized in that, described tensio-active agent is the polyoxyalkylene alkyl derivative.
6, the etching solution of copper as claimed in claim 1 is characterized in that, the content of ammonium oxalate is 0.05 weight %～5 weight %, and the content of hydrogen peroxide is 0.2 weight %～10 weight %, and the content of tensio-active agent is 0.0001 weight %～5 weight %.
7, the etching solution of copper as claimed in claim 1 is characterized in that, it is the etching solution that copper under the coexistence of the metal with superior electrical conductivity that distribution or electrode are used or copper alloy carry out selective etch.
8, the etching solution of copper as claimed in claim 7, it is characterized in that the metal with superior electrical conductivity that distribution or electrode are used is that to be selected from by aluminium, titanium, nickel, tin, lead, silver, gold, palladium with more than one these metals be one or more material in the group of alloy composition of main composition.
9, the etching solution of copper as claimed in claim 1 is characterized in that, the etching solution of described copper uses 20 ℃～50 ℃ temperature.
10, the etching solution of copper as claimed in claim 1, it is characterized in that, it is the etching solution that mixes the copper for preparing by the effective constituent that will contain ammonium oxalate, hydrogen peroxide and tensio-active agent at least with water, wherein with the effective constituent beyond the hydrogen peroxide with after water mixes, interpolation and mixing hydrogen peroxide obtain the etching solution of this copper in this mixture.
11, a kind of engraving method, it is under the coexistence of the metal with superior electrical conductivity that distribution or electrode are used, the method of selective etch copper or copper alloy, it is characterized in that, the etching solution that uses contains ammonium oxalate, hydrogen peroxide and tensio-active agent at least, and the surface tension of etching solution is below the 45mN/m, and pH is 6.0～8.5.
12, engraving method as claimed in claim 11 is characterized in that, described etching solution also contains amino acid, and amino acid whose content is 0.2 weight %～25 weight %.
13, engraving method as claimed in claim 12 is characterized in that, described amino acid is glycine.
14, engraving method as claimed in claim 11 is characterized in that, described tensio-active agent is to have to be selected from by-SO
3The M base ,-OSO
3M base and-in the group that the COOM base is formed one or more functional group aniorfic surfactant and/or have the nonionic surface active agent of the repeat unit structure of oxyalkylene, wherein, M represents alkali metal or hydrogen atom.
15, engraving method as claimed in claim 14 is characterized in that, described tensio-active agent is a polyoxyalkylene alkyl.
16, engraving method as claimed in claim 11, it is characterized in that, the content of the ammonium oxalate of described etching solution is 0.05 weight %～5 weight %, and the content of hydrogen peroxide is 0.2 weight %～10 weight %, and the content of tensio-active agent is 0.0001 weight %～5 weight %.
17, engraving method as claimed in claim 11, it is characterized in that the metal with superior electrical conductivity that distribution or electrode are used is that to be selected from by aluminium, titanium, nickel, tin, lead, silver, gold, palladium with more than one these metals be one or more material in the group of alloy composition of main composition.
18, engraving method as claimed in claim 11 is characterized in that, carries out etching 20 ℃～50 ℃ temperature.
19, engraving method as claimed in claim 11, it is characterized in that, described etching solution is to mix the etching solution for preparing with water by the effective constituent that will contain ammonium oxalate, hydrogen peroxide and tensio-active agent at least, wherein with the effective constituent beyond the hydrogen peroxide with after water mixes, interpolation and mixing hydrogen peroxide obtaining this etching solution in this mixture.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2005/005976 WO2006103751A1 (en) | 2005-03-29 | 2005-03-29 | Copper etchant and method of etching |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101098989A true CN101098989A (en) | 2008-01-02 |
Family
ID=37053025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200580046553XA Pending CN101098989A (en) | 2005-03-29 | 2005-03-29 | Copper etchant and method of etching |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101098989A (en) |
| WO (1) | WO2006103751A1 (en) |
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