TW200936811A - Etching solution and method of producing copper wirings using the same - Google Patents

Abstract

The invention provides an etching solution capable of producing copper wirings having few undercuts and depressions and having excellent linearity, and a method of producing the copper wirings using the etching solution. The etching solution of the invention is a copper etching solution, which contains acids, bivalent copper ion sources, tetrazoles, and water, and contains a polymer whose structural unit has a functional group represented by the following formula (I).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching solution for copper and a method for forming a copper wiring using the same, the copper etching solution comprising an acid, a source of divalent copper ions, and a silicon germanium. Class and water. [Prior Art]

V In the production of a printed wiring board, when a copper wiring pattern is formed by photolithography, a vaporized iron-based etching solution, a vaporized copper-based etching solution, an alkaline etching solution, or the like can be used as the etching liquid. When such an etching liquid is used, copper under the etching agent called undercut is dissolved from the side surface of the wiring pattern. That is, the following phenomenon (undercut) originally intended to be removed by etching with a resist to be removed by etching (ie, the wiring portion) is removed by side etching, and along the bottom to the top of the wiring, the width In particular, when the wiring pattern is fine, it is necessary to make the undercut as small as possible. In order to suppress the undercut, for example, an etching liquid or an etching method described in Patent Documents 1 to 6 below has been proposed.底, the undercutting force of the engraving liquid or the residual method I described in Patent Documents 1 to 6 is not sufficient, and therefore an etching solution or an etching method which requires an undercutting suppression force in the market is required. In the following, Patent Document Nos. 7 and 8 have been proposed to prepare an etchant having a high undercutting suppression force by using a shoe of the right 丨 丨 haiji. Patent Document 1: Patent 1 专利 矛 矛 矛 特Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-23338. 〇6784 bulletin Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2, No. Hei. Patent Document Laid-Open No. 2005-330572. SUMMARY OF THE INVENTION D The undercut is suppressed by the etching liquids of the above-mentioned Patent Documents 7 and 8. However, if the surname is used in the usual method, a depression is formed on the side of the copper wiring. Or if the shape is uneven. If a recess is formed on the side of the copper wiring, the current or the electrical signal cannot be stably turned on, and the wiring width cannot be accurately checked. That is, the inspection of the wiring width is usually from the printed wiring board. The upper side optically detects the difference in reflectance between the copper surface and the substrate surface, and obtains the top width of the copper wiring. However, when the side surface of the copper wiring is recessed, the thinnest portion (intermediate portion) of the wiring width is in the self-printing wiring board. The upper inspection is hidden at the top, so the wiring width cannot be accurately checked. If the shape of the copper wiring is uneven, the linearity of the copper wiring is reduced, and the printed wiring board is removed. In the above, the optical width of the wiring width is incorrectly recognized. In particular, in the printed wiring board, the distance between the thin line portions formed on the COF (Chip On Film) substrate may be 20 to 30#. The optical inspection error when the wiring width is about 5 to 13 cm, and the optical inspection of the copper wiring is low is recognized as 4 200936811. The present invention provides a problem that overcomes the disadvantages of the prior art and can be formed. An etching solution for copper wiring having less undercut and recess and excellent linearity, and a method for forming a copper wiring using the etching liquid. The etching liquid of the present invention comprises an acid, a divalent steel ion source, a tetrazole, and water. The etching solution for copper is characterized by comprising a polymer having a functional group represented by the following formula (I) in a constituent unit.

Ο (1) Further, the etching liquid of the present invention is an etching solution for copper, but the "copper" includes not only pure copper but also a copper alloy. Further, in the present specification, "copper" means pure copper or a copper alloy. Further, the method of forming a copper wiring according to the present invention is a method of forming a copper wiring which etches a portion of a steel layer which is not covered with a corrosion inhibitor, and is characterized in that etching is performed using the etching liquid of the present invention. Since the money engraving liquid of the present invention contains a polymer having a functional group represented by the above formula (1), it is possible to form a copper wiring having less undercut and depression and excellent linearity. Further, according to the copper wiring of the present invention, the etching liquid of the present invention is used, so that a copper wiring having a bottom portion, a small M ^ s ^ ^ A w trap, and excellent linearity can be formed. [Embodiment] The etching liquid of the present invention is an etching liquid containing copper of acid or water, and is characterized by having a valence copper ion, a tetrazole, and a functional group represented by the above formula 5 (1). Polymer. Fig. 1 is a partial cross-sectional view showing an example of a copper wiring which is etched by the etching liquid of the present invention. A corrosion inhibitor is formed on the copper wiring 1 and a protective film 3 is formed on the side surface of the copper wiring 1 directly under the end of the resist 2, and the protective film 3 is mainly formed in the etching liquid while being etched. A valence steel ion and a salt thereof, a tetrazole, and the above polymer are formed. Since the surname liquid of the present invention contains the above polymer, the density of each component contained in the protective film 3 is increased, and the denseness of the protective film 3 is improved. © Therefore, since the etching liquid can be prevented from entering the protective film 3 during etching, the undercut can be prevented as compared with the etching liquid immediately before. Further, even if the protective film 3 is formed, the undercut can be sufficiently suppressed, so that the depression can be surely prevented, the linearity of the copper wiring 1 can be improved, and the short circuit between the copper wirings 1 can be suppressed. In the present invention, the structure for forming the protective film 3 while etching is as follows. First, copper (not shown) which is not covered by the inhibitor 2 is etched by the divalent copper ions and the acid. At this time, in the etching solution, monovalent copper ions are generated by the reaction of the divalent copper ions with the etched metal steel. The valence copper ion dissolves and diffuses in the etching solution at a low concentration. However, when the etching progresses to a high concentration, the bond is formed by bonding with the scorpion contained in the button etchant. Conjuncts. The insoluble matter mainly composed of the bonded body adheres to the side surface of the copper wiring 1 to form a protective skin of $3, and the etching of the portion is suppressed. In the case of using hydrochloric acid, if the monovalent copper ion is at a high concentration, the vaporized ions in the etching solution J are ion-bonded to precipitate insoluble vaporized cuprous crystals, and the above H @ is attached to the side of the copper wiring 1 Forming a strong protection 6 200936811 Thick film 3 gj This is in the part where the higher concentration of copper ions is suppressed, and the etching is performed in the lower part of the concentration of copper ions. Furthermore, after the etching process The protective film 3 can be easily removed by a treatment using a removal liquid. The removal liquid is preferably an acidic liquid such as hydrochloric acid, a mixture of hydrogen peroxide and sulfuric acid, or an organic solvent such as dipropylene glycol monomethyl ether or the like. The acid component of the rice broth may be appropriately selected from the inorganic acid and the organic acid. The concentration of the acid is preferably 7 to 180 g/L, more preferably 18 to 110 g/L. It is accelerated, so that the copper coins can be quickly engraved. Further, by using δ to be 18 〇g/L or less, the dissolution stability of copper can be maintained and the reoxidation of the steel surface can be prevented. As the above inorganic acid, sulfuric acid can be cited. , hydrochloric acid, nitric acid, phosphoric acid, etc. as the above organic Examples of the acid include citric acid, acetic acid, oxalic acid, maleic acid, benzoic acid, and glycolic acid. Among the above acids, hydrochloric acid is preferred from the viewpoints of stability of etching rate and dissolution stability of copper. Specific examples of the source of the divalent copper ion contained in the surname of the present invention include: vaporized copper, copper sulfate, copper bromide, copper salt of an organic acid, copper hydroxide, etc., particularly In the case of copper chloride (secondary copper oxide), the etching rate is increased, so that the concentration of the above-mentioned divalent copper ion source is preferably from 4 to I55 g/L, more preferably from 6 to 12.5 g/L. 122g/L. When the thickness is 4g/L· or more, the etching rate is increased, so that the copper can be quickly etched. Further, by setting the 疋 to 155 g/L or less, the dissolution stability of copper can be maintained. In the case of copper, the concentration of the second vaporized copper is preferably 8 to 33 〇g/L, more preferably 13 to 260 g/L. The etchant of the present invention is used to form a pattern having a different wiring interval. In the copper wiring pattern of the region, the concentration of the divalent copper ions in the etching solution is preferably 6 to 56 g/L, more preferably 24~4〇g/I^ If a plurality of pattern regions having different wiring intervals are formed at the same time by using the previous etching liquid, the etching time is longer than the pattern region where the wiring interval is narrower and the wiring interval is wider. Therefore, there is a case where, in a pattern region where the interval is narrower, at the time point when the etching is finished, the copper layer of the pattern region having a wide interval is in an excessively etched state, and the bottom of the pattern is thinned. Fine, there is a slogan that the adhesion between the pattern and the substrate is reduced; or the bottom of the pattern cannot be confirmed from above the pattern when the price is evaluated; or the upper part of the pattern is invaded in the subsequent step A pattern defect or the like is caused. In this case, in the etching solution of the present invention, by performing the divalent copper ion spread in the etching liquid to be 56 g/L or less, it is possible to suppress excessive etching of the pattern region having a wide interval. This prevents the bottom of the pattern from becoming thinner. Further, by making the copper ion/agronomy in the etching solution 6 g/L or more, the processing time of the surname can be shortened. In the above, the "copper wiring pattern having a plurality of pattern regions having different wiring intervals" may include, for example, at least a 图案1 pattern region and a second pattern region having a narrower interval between wirings than the first pattern region. Copper wiring pattern. Examples of the tetrazole contained in the residual liquid of the present invention include tetrazole, a derivative thereof, and the like. For example, m tetrasodium, 5-amino group _ih four-seat, and 5-methyl-1H·tetra are mentioned. Sit, 5·stupyl-1H tetrazole, 5_mercapto_ih_tetrazole, 1-phenyl-5-sulfonyl-1H-tetrazole, cyclohexyl_5-sulfonyl-ih_tetrazole, 5 , 5, _ bis-1H-tetrazole-diammonium salt, and the like. Among them, preferred is 1H-tetrazole, 5-amino-1H_tetrado-5-phenyl-1H-tetrasodium, 5,5·_bis-1H_tetrazole-diammonium salt, more preferably 8 200936811 1Η- Four saliva, 5-amino-1Η-tetrasal. The increase of the above four flavors is preferably from 0.1 to 50 g/L, more preferably (Μ~15g/L' is preferably 〇.2~1〇g/L. Within the range, the undercutting suppression function can be fully utilized in the cost of reducing the speed of (4). 四 四 The tetrasaloid can be used in the etching solution of the present invention. The tetrasaline has 4 atmosphere atoms in the ring. The number of atoms is more than that of other ruthenium, so it is considered that tetrazolium plaques are more easily combined with copper than other azoles. The inventors have found that a combination of tetrazole and valence copper ions can form a firm and uniform protective film... According to the invention, by combining the tetrazole and the polymer, a copper wiring pattern having a wide top width, a small undercut, no short circuit, and good linearity can be formed. The constituent unit has the above formula (1). Specific examples of the polymer of the functional group include poly(ethylene biguanide) represented by the following formula (π), poly(ethyleneimine biguanide) represented by the following formula (8), and polycondensation represented by the following formula (Iy). (hexamethylene biguanide) a dicyanodiamine-diethylenetriamine polycondensate represented by the following formula (V), which is represented by the formula (VI) Poly(sodium arginine amide), dicyandiamide-formaldehyde polycondensate represented by the following formula (fox), dicyanodiamine-three as shown by the following formula (view) Ethylenetetramine polycondensate and the like.

.--(II)

9 200936811

Among them, a polymer having a tertiary nitrogen atom as the above functional group or a polymer containing a fourth-order nitrogen as the above functional group is preferred. This is because the denseness of the formed protective film is further improved, so that copper wiring having less undercut and recess and more excellent linearity can be formed. The above-mentioned third-stage nitrogen-containing polymer can be exemplified by: dicyanodiamine-diethylenetriamine polycondensate, dicyanodiamine- 10 200936811 曱polycondensate, dicyanodiamine-triethylenetetramine Polycondensate, etc. Further, the above-mentioned polymer containing a quaternary gas may, for example, be a dicyanodiamine-polycondensate. The concentration of the above polymer is preferably 〇1〇〇1〇g/L, more preferably 0.002~lg/L. When it is in the above range, the function of improving the density of the protective film can be sufficiently exhibited without lowering the etching rate. The weight average molecular weight of the above polymer is preferably 70.4 million, more preferably 800 to 70,000. When it is in the above range, the function of improving the post-release property of the protective film can be sufficiently exhibited without impeding the solubility of the above polymer. In addition to the above components, other components may be added to the etching liquid of the present invention to the extent that the effects of the present invention are not impaired. For example, a component stabilizer, an antifoaming agent, or the like can be added. The above etching solution can be easily prepared by dissolving each of the above components in water. The water is preferably water having ionic substances or impurities removed, and is preferably, for example, ion-exchanged water, pure water, ultrapure water or the like. The above etchant may be formulated so as to achieve a specific concentration at the time of use, and the concentrate may be prepared in advance and diluted before use. The method of using the etching solution is not particularly limited, and in order to effectively suppress undercut, it is preferable to perform etching using a nebulizer as described later. Further, the temperature of the etching liquid at the time of use is not particularly limited, and it is preferably used at 20 to 5 51 in order to maintain productivity and to effectively suppress undercut or depression. Next, a method of forming the copper wiring of the present invention will be described. The method of forming a copper wiring according to the present invention is a method of forming a copper wiring which is etched by a portion of a copper layer which is not covered with a silver barrier, and is characterized by etching using the etching solution of the present invention. As a result, as described above, the shape of the 200936811 is reduced to copper wiring with less undercut and excellent linearity.

In the method for forming a copper wiring according to the present invention, it is preferred that the etching liquid is sprayed on a portion of the copper layer not covered with a corrosion inhibitor by a spray. The reason is that it can effectively suppress the undercut. In particular, if a fan-shaped nozzle sprayer is used, the surname engraving can be sprayed to flow through the surface of the material to be etched in a fixed direction, and thus the copper ion concentration in the surname of the engraving liquid near the center of the copper wiring is compared. It is possible to increase the concentration of one of the copper ions in the etching liquid near the side of the copper wiring. As a result, etching is performed without forming a protective film between the copper wirings, and a protective film is formed in the vicinity of the side surface of the copper wiring to suppress etching. Therefore, etching is suppressed directly under the resist, so that undercut can be surely prevented. In addition, as for the fan-shaped nozzle sprayer, for example, the Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The one described in Japanese Laid-Open Patent Publication No. Hei 7-273153, and the like. When the remaining time is carried out by a sprayer, the spray pressure of the sprayer in the remainder is preferably G.04 MPam. (4) If the spray pressure is within the range, the thickness may be appropriately (described later). The side of the copper wiring forms a protective skin. Therefore, the undercut can be effectively prevented, and the residue of the purely indented portion can be prevented. Further, from the viewpoint of preventing damage of the corrosion inhibitor, the above pressure is preferably 〇3 MPa or less. Further, when the button is engraved by the atomizer, for example, when the material to be etched is transferred by the production line of the surname, the etching liquid which is initially scattered in the etching treatment device may adhere to the etched material. lI ^ ^ After the material is etched, the material to be etched is transferred to the atomizer to start etching. At this time, the etching liquid adhering to the copper surface is stagnant immediately before the spray 12 200936811, and thus the protective film is formed before the start of etching and the subsequent etching is hindered. As a result, there is an unetched portion remaining between the copper wirings, and a short circuit occurs. In order to improve this, it is preferred to use an etching method in which the residual liquid adhered to the surface of the steel is not circulated and the residence time can be shortened. Specifically, it is preferable that the etching is started from the time when the etching liquid is initially adhered to the surface of the copper layer to within 14 seconds, and the etching is started at a spray pressure of 0.4 MPa or more. In order to set this range, for example, the transfer speed of the material to be etched may be adjusted. In the method of forming a copper wiring according to the present invention, it is preferable to form a protective film of an appropriate length and thickness on the side surface of the copper wiring. The proper length of the protective film is as follows: In the protective film 3 of Fig. i, the length a in the thickness direction of the copper wiring turns is 20% or more of the thickness b of the copper wiring 1. If it is this range, undercut or depression can be effectively prevented. Further, in order to effectively suppress the depression, the length a is preferably 5% or more, more preferably 8% or more, and most preferably 100% of the thickness b. Further, the appropriate thickness of the protective film refers to the case where the maximum thickness C in the protective film 3 of Fig. i is 0.4 # m or more and less than 5 〇. If it is in this range, the undercut can be effectively suppressed, and the copper wiring is good in linearity. Further, if it is in this range, the protective film 3 is deposited between the copper wirings, and the short circuit caused by the unmarking can be prevented. Further, in order to make the protective film of an appropriate length and thickness as described above, it can be achieved, for example, by disposing the above-mentioned tetrazoles in an etching solution in a preferred concentration range. Further, the above control of the length and thickness can be achieved by adjusting the etching conditions (spray pressure, processing temperature, etching time, etc.). 13 200936811 The method for forming a copper wiring according to the present invention can be used for forming various patterns, and can effectively serve as a copper wiring pattern including a first pattern region and a second pattern region having a narrower interval between wirings than the first pattern region. The method of formation. Here, as described above, in order to suppress excessive etching of the steel layer in the first pattern region, the etching liquid used has a divalent copper ion concentration of preferably 6 to 56 g/L, more preferably 24 to 40 g/L. In particular, it can be effectively used in a method of forming a copper wiring pattern in which the interval between wirings in the first pattern region is D1 and the interval between wirings in the second pattern region is D2. 'D1 minus D2 is 7/zm or more. [Examples] Hereinafter, examples of the etching liquid of the present invention will be described together with comparative examples. Furthermore, the present invention is not limited to the ones described in the following embodiments. Each of the etching liquids having the compositions shown in Table 1 was prepared and etched under the conditions described later, and each item was evaluated by the evaluation method described later. Each etching solution was prepared in the following manner: First, after dissolving hydrochloric acid in ion-exchanged water, the remaining components were added. Further, the concentration of hydrochloric acid shown in Table 1 is the concentration in terms of hydrazine gasification. Further, the numerical values in the parentheses of the polymers contained in the respective silver engraving liquids shown in Table 1 indicate the use of a vapor pressure type molecular weight measuring device manufactured by Gonotec Co., Ltd. at a sample concentration of 5% by weight (solvent: toluene). The weight average molecular weight measured under the conditions. (Test substrate used) A copper/polyimine laminate substrate having a copper layer thickness of 8 #m (manufactured by Sumitomo Metal Mining Co., Ltd., product name: S'PERFLEX) was prepared, and the photolithography method was used for the copper layer. A corrosion inhibitor pattern is formed. At this time, the thickness of the corrosion inhibitor is 4 200936811 private m, the spacing is 2 〇 #m, line / gap = 13 in m / 7 " m. (Etching conditions) The etching system is a nozzle sprayer using a fan nozzle sprayer (manufactured by IKEljchi Co., Ltd., product name VP9020) and a solid conical nozzle sprayer manufactured by Qkeuch I, product name: JJXP020). The reaction was carried out under the conditions of 0.12 MPa and a treatment temperature of 35 ° C. As for the processing time, it is set to 45 seconds in the fan-shaped nozzle sprayer, and a is again 3 5 seconds in the solid-cone nozzle sprayer. Thereafter, it was washed with water, dried, and evaluated as shown below. Further, the transfer speed of each test substrate was adjusted so that the time until the scattering liquid of the etching liquid first adhered to each test substrate to the start of etching at a spray pressure of 0.1 2 MPa was 9 seconds. (Measurement of Image by Scanning Electron Microscope (SEM)) A part of each substrate subjected to the surname treatment was cut, embedded in a cold-embedded resin, and polished to observe the cross section of the wiring. Further, the maximum thickness of the protective film, the length of the protective film in the thickness direction of the copper wiring (the length of the protective film), the top width of the copper wiring ©, the width of the bottom of the copper wiring, and copper were measured by image measurement of the SEM image. The width (intermediate width) of the narrowest part of the width of the middle portion of the wiring. Further, the protective film length/copper layer thickness ratio (%), the undercut amount, and the dent rate were calculated. Here, the undercut amount and the dent rate can be obtained by the following calculation formula. Undercut amount (# m) = {Line width of resister (13 in m) _ Top width of copper wiring (// m)} /2 Depression rate (Q/.) = (Top width of copper wiring - Copper The middle width of the wiring) / the top width of the copper wiring X1 〇〇 15 200936811 (Evaluation of the sensitivity by SEM) A part of the 2 〇 / zm pitch portion of each of the etched substrates was cut to form copper The surface of the protective film on the side of the wiring is exposed. The surface of the protective film was observed by sem. As for the compactness, the state of no defects, pores, and smoothness was evaluated as ◎, and the state of being non-smooth but not defective and the pores was evaluated as ?°, which was crystallized and varied in size. The defect or the hole is evaluated as x. Further, as an evaluation example of the compactness, SEM photographs (1 〇〇〇〇 times) of the surface of the protective film of Example 1 (〇), Example 4 (©), and Comparative Example 1 (x) are respectively shown in Figure 2, Figure 3 and Figure 4. (Measurement by Image of Optical Microscope) Each of the etched substrates was immersed in a 3 % aqueous sodium hydroxide solution for 60 seconds to remove the corrosion inhibitor. Thereafter, hydrochloric acid (hydrogenated hydrogen concentration: 7 wt%) was used, and a fan-shaped nozzle (manufactured by IKEUCHI Co., Ltd., product name: VP9020) was used, and the spray pressure was o. UMPa, the treatment temperature was 3 (rc, and the treatment time was 30). The protective film was removed in seconds, and an image of the top of the copper wiring was taken from the upper surface of the test substrate by an optical microscope to perform image measurement. When measuring the image, the wiring at 1 turn was measured at intervals of 5 // m. Width, the standard deviation is taken as the top linearity (^ m). Further, an image of the bottom of the copper wiring passing through the polyimide layer is taken from the bottom of the test substrate by an optical microscope, and image measurement is performed. In the case of the image, the wiring width at 1 测定 is measured at intervals of 5, and the standard deviation is taken as the bottom linearity (〆, and the presence or absence of the unetched portion is confirmed by observation with an optical microscope. 200936811

200936811

Disc 碡 碡 JO JO 5 JO 0.19 0.42 i 1 1- 0.15 1 0.39 1 0.12 0.35 0.83 0.73 0.13 0.19 0.55 0.59 0.12 0.19 0.10 0.19 0.09 0.20 0.26 0.38 0.14 0.16 0.30 0.47 d 10.2 I 10.6 1_ _ 10.2 i 10.1 10.8 10.5 10.9 10.8 〇1 - 10,5 〆CN vd CS 00 00 00 ΙΛ vd 〇\ m α; inch <NV) »〇CN inch CO r4 VO fN c<i 00 σ\ VO 00 ◎ ◎ ◎ ◎ ◎ ◎ XX ◎ ◎ 〇〇m 00 oo Ό 00 〇〇〇〇ο rj oo 00 fN 00 cn Os <Ν <si 〇»〇ο vd ΓΛ Ο) Os (Ν 0.005 <N o 280 § CN ο »〇•η 1 ο d II gasified copper hydrochloric acid 1H-tetradodecyldiamine-triethylenetetramine polycondensate (50000) copper hydride hydrochloride 5- 5-amino-1Η-tetrazole Di-n-butyldiamine-diethylenetriamine polycondensate (10000) copper dichloride hydrochloride 5-amino-1H-tetrazole dicyanodiamine-diethylenetriamine polycondensate (10000) Hydrochloric acid 1 1 Η-benzotriazole polyethylene glycol (4000) 2 gasified copper hydrochloric acid does not use polymer II copper hydride II acid 5-phenyl-1 Η-tetrazole 1 polyethylene yeast (2000) ' Example 5 Example 6 Example 7 Comparative Example 1 Vision 2 Comparative Example 3 200936811 As shown in Table 1, in Examples 1 to 7 of the present invention, good results were obtained for any of the evaluation items. In the examples 1 to 3, the results are inferior to those of the examples in the evaluation items. According to the results, it is understood that the copper wiring having less undercut and less depression and excellent linearity can be formed according to the present invention. Examples of copper wiring patterns in different two pattern regions are described. Each etching liquid having the composition shown in Table 2 is prepared and etched under the conditions described below. Each etching liquid can be prepared in the following manner: First, hydrochloric acid is dissolved © After ion-exchanged water, the remaining components were added. Further, the concentration of hydrochloric acid shown in Table 2 was determined by the concentration of hydrogen chloride. Further, in the parentheses of the polymers contained in the respective engravings shown in Table 2, The numerical value is a weight average molecular weight measured under the conditions of a sample concentration of 5% by weight (solvent: toluene) using a vapor pressure molecular weight measuring device manufactured by Gonotec. (Test substrate used) A copper/polyimine laminate substrate having a copper layer thickness of 8/m was prepared (product name: STERFLEX manufactured by Sumitomo Metal Mining Co., Ltd.), and formed on the copper layer by photolithography. Corrosion inhibitor pattern. At this time, the resist pattern is formed to have a thickness of 4//m, a line/space gap = 13 in a range of m/7#m, and a thickness of 4 m, line/gap = 32 " m/ 18; (a resist pattern in which the zm is 50 m-patterned area is mixed. (etching conditions) The etching system uses a fan-shaped nozzle sprayer (manufactured by IKEUchi Co., Ltd., product name: VP9020), and the spray pressure is 〇12 MPa, and the treatment temperature is 35. Under the conditions of 〇, the processing time at this time is shown in Table 2. Furthermore, the processing time 19 200936811 is set to 20 um between the rs·1 ^ & the bottom width of the copper wiring in the pattern area The time until 〇14#m was reached. The transfer speed of each test substrate was adjusted so that the time from the initial deposition of the silver sputum sputum to each test substrate to the start of etching at 0i2 MPa was 9 seconds. Thereafter, it is dried and 'valued by the same evaluation method as described above, and the bottom width of the "B_T" steel wiring of Table 2 is reduced by the value of the width of the price portion.

20 200936811

200936811 ❹ ❹ 墀 墀 κ κ s s VO VO <s ΙΛ> r4 ν-> inch·〇\ cs 〇〇ο Ο 〇ο 〇〇〇ο ! 10.4 1 26.9 11.6 29.5 iTi r4 30.4 j 10.8 _1 29,4 〇〇ΓΟ •-H 32.2 26.7 L 27.0 oo od 26.9 5 27.5 Ό σ< 28.0 ο CO 寸 m 2 oo <N <N <s <N 卜 cs 1 § <N| Ο »-Η <N 5 2 gasification of copper 5-amino-1H-tetrazole dicyanodiamine-diethylenetriamine polycondensate (10000) copper dioxide m 5-amine -1-1H-tetrazoledidecyldiamine-diethylenetriamine polycondensate (10000) copper dihydrogenated 5-amino-1H-tetrazoledi II-diamine-diethylenetriamine polycondensate (10000 2 gasified copper silver m 1H-benzotriazole polyethylene glycol (4000) copper dihydrate copper m 1H-benzotriazole polyethylene glycol (4000) Example 12 Example 13 Example 14 Comparative Example 4 Comparative Example 5 200936811 As shown in Table 9 όκΐ - ,, in Examples 9 to 14 in which the concentration of the divalent copper ions was 6 to 56 g/L, the copper in the pattern region of the 50 # m pitch could be made. Over-etching at the bottom of the wiring. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing an example of a copper wiring which is etched by the etching liquid of the present invention. Figure 2 is a SEM photograph of the surface of the protective film of Example 1. Figure 3 is a SEM photograph of the surface of the protective film of Example 4. 4 is a SEM photograph of the surface of the protective film of Comparative Example 1. Explanation of main component symbols] 1 2 3 a b c Steel wiring Corrosion protection coating The length of the protective film 3 along the thickness direction of the copper wiring 1 The thickness of the steel wiring 1 The maximum thickness of the protective film 3 23

Claims (1)

200936811 * VII. Patent application scope: 1' kind of silver engraving liquid' is an etching liquid containing an acid, a divalent copper ion source, a tetradron and a copper of water, and is characterized in that the constituent unit includes the following formula (1) The etchant of the above-mentioned functional group, wherein the functional group contains a tertiary nitrogen. The etching solution of claim 1, wherein the functional group contains a quaternary nitrogen. 4. The etching solution according to claim 1, wherein the polymer has a concentration of 0.001 to 1 g/L. 5. The etching solution according to claim 1, wherein the polymer has a weight average molecular weight of 700 to 100,000. 6. The etching solution according to claim 1, wherein the concentration of the divalent copper ions is 6 to 56 g/L. Ο 7. A method of forming a copper wiring by etching a portion of a copper layer which is not covered with a corrosion inhibitor, characterized in that etching is performed using an etching solution according to any one of claims 1 to 6 . 8. The method of forming a copper wiring according to claim 7, wherein the etching solution is sprayed by a sprayer to a portion of the copper layer which is not covered with a corrosion inhibitor. 9. The method of forming a copper wiring according to claim 8, wherein the atomizer is a fan-shaped nozzle atomizer. 24 « 200936811 10. The method for forming a copper wiring according to the eighth aspect of the patent application, wherein the spray pressure of the atomizer during etching is 0.04 MPa or more. 11. The method of forming a copper wiring according to the first aspect of the patent application, wherein, when spraying by the atomizer, the etching liquid is attached to the surface of the copper layer to within 14 seconds, . 喷雾 4MPa or more spray pressure begins ^ surname. 12. The method of forming a copper wiring according to claim 7, wherein the length of the protective film attached to the side of the copper wiring at the end of the etching along the thickness direction of the copper layer is 20 of the thickness of the copper layer. %the above. 13. The method of forming a copper wiring according to claim 7, wherein the maximum thickness of the protective film adhered to the side surface of the copper wiring at the end of the etching is 0.4 μm or more and less than 5.0/zm. The method of forming a copper wiring according to claim 7, wherein the pattern of the copper wiring includes a first pattern region and a second pattern region having a narrower interval than a gap between the wirings of the first pattern region. /"V, schema·* (such as the next page) 25