| Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents -> Monitor Keywords |
|
|
 
Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agentsRelated Patent Categories: Compositions, Electrically Conductive Or Emissive CompositionsAntistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents description/claimsThe Patent Description & Claims data below is from USPTO Patent Application 20070252111, Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents. Brief Patent Description - Full Patent Description - Patent Application Claims
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This is an application filed pursuant to 35 U.S.C. Section 111(a) with claiming the benefit of U.S. provisional application Ser. No. 60/618,569 filed Oct. 15, 2004, U.S. provisional application Ser. No. 60/618,571 filed Oct. 15, 2004 and U.S. provisional application Ser. No. 60/618,608 filed Oct. 15, 2004 under the provision of 35 U.S.C. 111(b), pursuant to 35 U.S.C. Section 119(e)(1). TECHNICAL FIELD [0002] The present invention relates to an antistatic treatment agent containing an aqueous solvent-soluble electroconductive polymer and a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound. More specifically, it relates to an antistatic treatment agent, which hardly forms a mixing layer with a chemically amplified resist employed in semiconductor microprocessing process while maintaining its antistatic property. Even more specifically, it relates to an antistatic treatment agent which exhibits an excellent wettability with a chemically amplified resist. Further, the present invention relates to an antistatic film, a coated article and a pattern forming method using the antistatic treatment agent. BACKGROUND ART [0003] A self-doping type electroconductive polymer is generally soluble in water and has characteristics of being easily formed in an arbitrary shape, formed in a film or positioned, and is therefore characterized with its extremely excellent workability in preparation of a large-area film or in an electrical device requiring microfabrication technology. [0004] A charge-up preventing technology utilizing such characteristics in a lithographic process employing charged particle beams such as electron beams of ion beams is disclosed (JP-A No. 4-32848) and is being widely employed recently. [0005] A chemically amplified resist, which is an essential material in common technology for lithography utilizing light or charged particle beams such as electron beams or ion beams, is a resist which is easily influenced by the use environment and is difficult to handle. [0006] In case of coating a surface of the chemically amplified resist with an electroconductive composition, it is already known that a slight acid component in the coating material can have a significant influence on the sensitivity of the resist. That is, phenomenons that under a certain hydrogen ion concentration (pH) range, acid generated by exposure is neutralized by the coating material and that acid supplied from the coating material makes an unexposed part fall in the same state as an exposed part are observed. Such a phenomenon appears as a film thickness loss in case of a positive type resist, while in case of a negative type resist, such a phenomenon appears as formation of a hardly soluble layer or an insoluble layer. [0007] For suppressing a pH change in an aqueous solution of an aqueous solvent-soluble electroconductive polymer, there is disclosed a method of eliminating oxygen dissolved in the solution (JP-A No. 8-259673) and a method of suppressing a pH decrease by using a buffer solution containing a weak acid and an amine (JP-A No. 11-189746). [0008] Recently there is encountered a problem of resist collapse, caused by reduction in the minimum circuit line width of a semiconductor device, and attempts are being made to select an appropriate aspect ratio in order to avoid such phenomenon, whereby resist film thickness tends to become smaller. A resist patterned through a developing step is subsequently used for a pattern transfer to a substrate by a dry etching step, and dry-etching resistance of the resist in this process is becoming more important, so that requirements for the prevention of a film thickness loss phenomenon of the resist caused by a charge-up preventing film and for the maintenance of a resist profile are becoming stricter in recent years. [0009] More specifically, in a process of forming an antistatic treatment film on a resist surface, in case where a solvent having a high affinity with water contained in the antistatic treatment agent remains in the resist, the liquid components show mutual penetration. As the aqueous solvent-soluble electroconductive polymer also migrates with the penetration of the liquid components, a mixing layer is formed at the interface between the resist and the antistatic treatment film. When the concentration of an acid component derived from the aqueous solvent-soluble electroconductive polymer contained in the mixing layer exceeds the concentration inducing a chemical change of the resist, there is exhibited a film thickness loss phenomenon in case of a positive chemically amplified resist, or formation of a hardly soluble layer or eventually a fogging phenomenon in case of a negative chemically amplified resist. Such an undesired chemical change at the interface generates a profile called a bowing or a T-top in the resist after patterning. In the process of transferring such pattern onto a substrate such as a silicon wafer, the development of such profile detrimentally affects control of variation in the line width and the depth and shape of etching, thus constituting a serious problem in fine patterning. [0010] It is known that since chemical amplification resists are mostly oil-soluble and a coated film thereof is not easily mixed with water, in case of coating a resist surface with an electroconductive composition, a surfactant is added to the electroconductive composition for the purpose of improving a wettability. However conventional surfactants that have been employed often cause an influence on the resist profile such as film thickness loss of the resist, while decrease in the amount of the surfactant reduces the wettability, thus affecting the coating property. On the other hand, since the surfactant also has an influence on the resist, there is disclosed a method of utilizing a water-soluble polymer having a surfactant effect (JP-A No. 2002-226721). DISCLOSURE OF INVENTION [0011] An object of the present invention is to provide an antistatic treatment agent having an ability of preventing resist film thinning phenomenon in a chemically amplified resist. Also another object is to provide an antistatic treatment agent having not only an ability of preventing resist film thinning phenomenon but also good coatability. Further, still another object of the present invention is to provide an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent. [0012] The present inventors, as a result of intensive investigations, have found that an antistatic treatment agent containing an aqueous solvent-soluble electroconductive polymer and a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound has an excellent ability for preventing film-thinning in a chemically amplified resist and have thus reached the present invention. The present inventors have further found out that if surfactant is added to the agent, the agent can maintain the ability of preventing film-thinning and exhibits excellent wettability, and have thus completed the present invention. [0013] Thus the present invention relates to a following antistatic treatment agent, a pattern forming method utilizing an antistatic film using the agent, and various substrate products obtained by utilizing the antistatic film and the pattern forming method. [0014] 1. An antistatic treatment agent comprising an aqueous solvent-soluble electroconductive polymer having a Bronsted acid group and a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound. [0015] 2. The antistatic treatment agent as described in item 1, further comprising a volatile basic compound. [0016] 3. The antistatic treatment agent as described in item 1, wherein the molar ratio of diamine (divalent) or polyamine (polyvalent) aliphatic basic compound in the total mole number of the basic compound is within a range of 0.1 to 75 mol. %. [0017] 4. The antistatic treatment agent as described in item 1, wherein at least one kind of the diamine (divalent) or polyamine (polyvalent) aliphatic basic compounds has a boiling point of 80.degree. C. or higher. [0018] 5. The antistatic treatment agent as described in item 1, wherein the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound consists of one or more kinds selected from a group of a diaminoalkane, a triaminoalkane, a polyaminoalkane and a polyalkylimine. [0019] 6. The antistatic treatment agent as described in item 5, wherein the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound consists of one or more kinds selected from a group of ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminodecane and polyethyleneimine. [0020] 7. The antistatic treatment agent as described in item 1, wherein the aqueous solvent-soluble electroconductive polymer is a .pi.-conjugated electroconductive polymer. [0021] 8. The antistatic treatment agent as described in item 1, wherein the Bronsted acid group is a sulfonic acid group. [0022] 9. The antistatic treatment agent as described in item 1, wherein the number of moles of the basic group contained in the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound is within a range of 0.05 to 50 mol % based on the number of moles of the Bronsted acid group contained in the aqueous solvent-soluble electroconductive polymer. [0023] 10. The antistatic treatment agent as described in item 2, which is an aqueous solution containing 0.1 to 10 mass % of an aqueous solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound and 0.1 to 20 mass % of a volatile basic compound, provided that the entire amount of the antistatic treatment agent is 100 mass %. [0024] 11. The antistatic treatment agent as described in item 1, further comprising a surfactant. [0025] 12. The antistatic treatment agent as described in item 11, wherein the surfactant is an anionic surfactant, an amphoteric surfactant or a mixture thereof. [0026] 13. The antistatic treatment agent as described in item 11, wherein the surfactant is an anionic surfactant. [0027] 14. The antistatic treatment agent as described in item 13, which is an aqueous solution containing 0.1 to 10 mass % of an aqueous solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound, 0.1 to 20 mass % of a volatile basic compound and 0.001 to 1 mass % of an amphoteric surfactant provided that the entire amount of the antistatic treatment agent is 100 mass %. [0028] 15. The antistatic treatment agent as described in item 1, wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (1): in the formula, m and n each independently represents 0 or 1; X represents S, N--R.sup.1 or O; A represents an alkylene group or an alkenylene group (that may have two or more double bonds) having 1 to 4 carbon atoms and having at least a substituent represented by -B-SO.sub.3.sup.-M.sup.+, wherein the alkylene and alkenylene group may be substituted with a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group or a substituted phenyl group; B represents --(CH.sub.2).sub.p--(O).sub.q--(CH.sub.2).sub.r-- in which p, q and r independently represents 0 or an integer of 1 to 3; and M.sup.+ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. [0029] 16. The antistatic treatment agent described in item 1, wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (2): in the formula, R.sup.2 to R.sup.4 each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a -B-SO.sub.3.sup.-M.sup.+ group; and B and M represent the same meanings as described in item 15. [0030] 17. The antistatic treatment agent as described in item 1, wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (3): in the formula, R.sup.5 represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a -B-SO.sub.3.sup.-M.sup.+ group; and B, p, q, r and M represent the same meanings as described in item 10. [0031] 18. The antistatic treatment agent described in item 1, wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (4): in the formula, R.sup.6 to R.sup.8 each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a SO.sub.3.sup.-M.sup.+ group; R.sub.9 represents a hydrogen atom or a monovalent group selected from a group of a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group; and B and M represent the same meanings as described in item 15. [0032] 19. The antistatic treatment agent as described in item 15 or 16, wherein the aqueous solvent-soluble electroconductive polymer is a polymer including 5-sulfonisothianaphthene-1,3-diyl as a chemical structure. [0033] 20. An antistatic film obtained by using the antistatic treatment agent as described in any one of the items 1 to 19. [0034] 21. A coated article coated with the antistatic film as described in item 20. [0035] 22. A coated article described in item 21, wherein the antistatic film is formed on a photosensitive composition or a charged particle-sensitive composition coated on a base substrate. [0036] 23. The pattern forming method using the antistatic film as described in item 20. [0037] Moreover, the invention relates to a following aqueous solution. [0038] 24. An aqueous solution for antistatic treatment agent comprising a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound and an anionic surfactant. [0039] 25. An aqueous solution for antistatic treatment agent comprising a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound, a volatile basic compound and an anionic surfactant. [0040] 26. The aqueous solution for antistatic treatment agent as described in item 24 or 25, wherein the mole fraction of the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound is within a range of 0.1 to 75 mol % based on the total number of moles of the basic compounds. [0041] 27. The aqueous solution for antistatic treatment agent as described in any one of items 24 to 26, comprising at least one kind of the diamine (divalent) or polyamine (polyvalent) aliphatic basic compounds having a boiling point of 80.degree. C. or higher. [0042] 28. The aqueous solution for antistatic treatment agent as described in any one of items 24 to 27, wherein the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound consists of one or more kinds selected from a group of a diaminoalkane, a triaminoalkane, a polyaminoalkane and a polyalkylimine. [0043] 29. The aqueous solution for antistatic treatment agent as described in any one of items 24 to 27, wherein the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound consists of one or more kinds selected from a group of ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminodecane and polyethyleneimine. BEST MODE FOR CARRYING OUT THE INVENTION [0044] The antistatic treatment agent contains an aqueous solvent-soluble electroconductive polymer, and a coating film using the agent and an article coated with the agent having electroconductivity are used for antistatic purpose. [0045] The antistatic treatment agent of the invention, if left standing or dried after an application, loses its water content through evaporation or the like, thereby becoming a semi-solid or a solid without fluidity. The agent in such a state with no fluidity is called "antistatic material", and the antistatic material in a film state is called an "antistatic film". The present invention will be further clarified in the following. [0046] The aqueous solvent-soluble electroconductive polymer is generally a .pi.-conjugated electroconductive polymer having a Bronsted acid group, and is used in a state where a sulfonic acid group or a carboxylic acid group derived from the Bronsted acid group is neutralized with a basic compound. In the present invention, the neutralization is conducted with a mixture consisting of a diamine (divalent) or polyamine (polyvalent) basic compound or another basic compound. [0047] The aqueous solvent-soluble electroconductive polymer, after being coated on a resist surface, forms an ionic bond with a basic compound along with the evaporation of water, but does not lose mobility completely. Also in case of employing a volatile basic compound, when the base substrate is heated together with the resist coated with antistatic film, the ionic bonds formed with the volatile basic compound are partially decomposed to thereby allow the base component to evaporate, thereby resulting in a drawback that a Bronsted acid thus generated affects the resist. [0048] The present inventors have found out that, by neutralizing Bronsted acids in the aqueous solvent-soluble electroconductive polymer with a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound, ionic bonds are formed between the electroconductive polymer and the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound in the antistatic film formed on the surface of the resist film, thereby suppressing mobility of the electroconductive polymer in the antistatic film to thereby prevent mixing at the interface with the chemically amplified resist and that it is effective for suppressing film thickness loss and for maintaining the resist profile. Continue reading about Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents... Full patent description for Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents Brief Patent Description - Full Patent Description - Patent Application Claims Click on the above for other options relating to this Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents patent application. ###  How KEYWORD MONITOR works... a FREE service from FreshPatents1. Sign up (takes 30 seconds). 2. Fill in the keywords to be monitored. 3. Each week you receive an email with patent applications related to your keywords. Start now! - Receive info on patent apps like Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents or other areas of interest. ### Previous Patent Application: Inorganic light-emitting materials for uv solid light source Next Patent Application: Nano compounds and organic memory devices comprising the same Industry Class: Compositions ### FreshPatents.com Support Thank you for viewing the Antistatic treatment agent, and antistatic film, coated article and pattern forming method using the agents patent info. IP-related news and info Results in 0.11682 seconds Other interesting Feshpatents.com categories: Daimler Chrysler , DirecTV , Exxonmobil Chemical Company , Goodyear , Intel , Kyocera Wireless , 174 |
 * Protect your Inventions * US Patent Office filing 
PATENT INFO |
|
