JP5988151B2 - Manufacturing method of three-dimensional multilayer structure - Google Patents

Description

The present invention relates to the preparation how the 3D multilayer structure using a photosensitive metal complex.

  In recent years, research on manufacturing a three-dimensional multilayer structure having a complicated structure on a substrate by making full use of thin film technology has been advanced. For example, rf switches, cantilevers and the like are manufactured by a wafer process using MEMS technology.

  However, for example, a complicated process such as sacrificial layer etching is required to produce a structure having a cavity inside.

  In addition, in Japanese Unexamined Patent Application Publication No. 2011-207693, the inventors applied different metal complex photosensitive films to the front surface / back surface of the substrate, and used each of the metal complex films with light of different wavelength bands. A method of forming a metal oxide film pattern on both sides by pattern exposure is disclosed.

  JP-A 2010-256706, US Patent Application Publication No. 2011/0064913 and US Pat. No. 594376 disclose various photosensitive complexes.

JP 2011-207693 A JP 2010-256706 A US Patent Application Publication No. 2011/0064913 US Pat. No. 594376

Embodiments of the present invention aims to provide easily a three-dimensional multilayer structure three-dimensional multi-layer structure can be produced manufactured how.

  In the method for manufacturing a three-dimensional multilayer structure according to the embodiment of the present invention, when light in the first wavelength band is received by the substrate, light in the second wavelength band having a longer wavelength than the first wavelength band is received. A first coating step of coating a first photosensitive film containing a first metal complex whose solubility in a developer greatly changes, and light including the first wavelength band, A second exposure film comprising: a first exposure step for pattern exposure; and a second metal complex that changes its solubility in the developer when receiving light in the first wavelength band and the second wavelength band. A second coating step for coating on one photosensitive film; a second exposure step for pattern-exposing the second photosensitive film with light that includes the second wavelength band but does not include the first wavelength band; And developing the first photosensitive film and the second photosensitive film using the developer. That includes a developing step.

According to an embodiment of the present invention can provide a manufacturing how readily 3D multilayer structure three-dimensional multi-layer structure can be produced.

It is a flowchart of the manufacturing method of the three-dimensional multilayer structure of embodiment. It is a schematic diagram for demonstrating the manufacturing method of the three-dimensional multilayered structure of embodiment. It is a graph which shows the light absorption characteristic of the photosensitive film | membrane used for the manufacturing method of the three-dimensional multilayer structure of embodiment. It is a graph which shows the spectral characteristic of the ultraviolet lamp used for the manufacturing method of the three-dimensional multilayer structure of embodiment. It is a perspective view of the three-dimensional multilayer structure of an embodiment. It is a perspective view of the three-dimensional multilayer structure of an embodiment.

  Hereinafter, the manufacturing method of the three-dimensional multilayer structure and the three-dimensional multilayer structures 1 and 2 according to the embodiment will be described with reference to the flowchart shown in FIG.

<Step S10> Preparation of Photosensitive Metal Complex Solution First, two types of photosensitive metal complex solutions are prepared. The photosensitive metal complex is produced by reacting the synthesized ligand with a metal compound.

  The first ligand, 4- (2-nitrobenzyloxycarbonyl) catechol (I) (hereinafter referred to as “NBOC-CAT”), is obtained by converting 3,4-dihydroxybenzoic acid into a 2-nitrobenzyl alcohol derivative. Alternatively, it was synthesized by esterification with a 2-nitrophenethyl alcohol derivative.

  Next, NBOC-CAT (4.05 g), the first ligand, was dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), and tetraisopropoxide titanium (2.07 mL). Was added and heated at 100 ° C. for 1 hour to obtain a coating solution of the first photosensitive metal complex (NBOC—Ti).

  On the other hand, the second ligand 4- (4,5-dimethoxy-2-nitrobenzyloxycarbonyl) catechol (hereinafter referred to as “NVOC-CAT”) is 4,5-dimethoxy-2-nitrobenzyl alcohol. Was then brominated to synthesize 4,5-dimethoxy-2-nitrobenzyl bromide and reacted with 3,4-dihydroxybenzoic acid.

  Next, the second ligand, NVOC-CAT (2.10 g) and nickel acetate tetrahydrate (1.5 g) were added to ethyl lactate (16 mL) and N, N′-dimethylacetamide (4 mL). This was dissolved at 0 ° C. to obtain “Solution A2”. On the other hand, NVOC-CAT (0.35 g), 2-methoxyethoxyacetic acid (0.08 mL) and 2-aminoethanol (0.05 g) were dissolved in ethyl lactate (2 mL) and acetone (2 mL), and palladium acetate (0.225 g) was added and dissolved with an ultrasonic cleaner to obtain “Solution B2.” “Solution A2” and “Solution B2” were mixed together to obtain a coating solution of the second photosensitive metal complex (NVOC-NiPd). That is, the second photosensitive metal complex is a mixture of a Ni complex and a Pd complex.

  The first photosensitive metal complex (NBOC and the like) and the second photosensitive metal complex (NVOC and the like) both have so-called positive photosensitivity that greatly increases the solubility in an alkali developer when receiving short-wavelength light. Have sex.

<Step S11> First Application Step As shown in FIG. 2A, the first metal complex solution is coated using a spin coating method and dried at 100 ° C. for 10 to 60 minutes. A first photosensitive film 21 made of a first photosensitive metal complex (NBOC-Ti) was applied on the surface.

<Step S12> First Exposure Step As shown in FIG. 3, the first photosensitive film 21 has an absorption band in the first wavelength band (λ1 = 280 nm to 320 nm). “280 nm to 320 nm” means “over 280 nm and below 320 nm”. For this reason, as shown in FIG. 2B, light including the first wavelength band is subjected to pattern exposure through a photomask 31, and an exposure region 21 A is formed in the first photosensitive film 21. For the exposure, an ultraviolet lamp having the spectral characteristics shown in FIG. 4 was used. The exposed area 21A is easily dissolved in an alkali developer.

<Step S13> Second Coating Step As shown in FIG. 2C, the second metal complex solution is coated using a spin coating method and dried at 100 ° C. for 60 minutes, whereby the first photosensitive film is formed. A second photosensitive film 22 made of a second photosensitive metal complex (NVOC-NiPd) was applied to the surface of 21. Although the first photosensitive film 21 has been subjected to pattern exposure, but has not been developed, the surface thereof is flat. For this reason, it is easy to apply the film thickness of the second photosensitive film 22 uniformly. In addition, even if it heats again in a 2nd application | coating process, the solubility of the exposure area | region 21A of the 1st photosensitive film | membrane 21 does not change.

<Step S14> Second Exposure Step As shown in FIG. 2D, through the photomask 32, the second wavelength band (λ2 = 320 nm to 400 nm) and the first wavelength band (λ1 = 280 nm to 320 nm) are included. The second photosensitive film 22 was subjected to pattern exposure with light containing no exposure to form an exposure region 22.

  That is, the second exposure process was performed by disposing a short wavelength cut filter for cutting light of less than 320 nm on the ultraviolet lamp having the spectral characteristics shown in FIG.

  As shown in FIG. 3, the second photosensitive film 22 also has an absorption band in the second wavelength band (λ2). For this reason, the exposure region 22A of the second photosensitive film 22 is changed to be easily soluble in the alkaline developer.

  Note that the first photosensitive film 21 under the second photosensitive film 22 also receives light in the second wavelength band (λ2) in the second exposure step. However, as shown in FIG. 3, the first photosensitive film 21 has almost no absorption in the second wavelength band (λ2) longer than the first wavelength band (λ1). That is, when the first photosensitive film 21 receives light in the first wavelength band (λ1), the first photosensitive film 21 receives light in the second wavelength band (λ2) longer than the first wavelength band (λ1). , The solubility in the developer changes greatly. For this reason, even if the unexposed area | region of the 1st photosensitive film | membrane 21 is exposed in a 2nd exposure process, it is hardly soluble with respect to a developing solution.

<Step S15> Development As shown in FIG. 2E, when developed using an alkaline developer, the exposed region 21A of the first photosensitive film 21 and the exposed region 22A of the second photosensitive film 22 are dissolved. A three-dimensional multilayer structure 1 is produced.

  That is, the three-dimensional multilayer structure 1 including the second photosensitive film 22 patterned in a pattern different from the first photosensitive film 21 is formed on the patterned first photosensitive film 21. The three-dimensional multilayer structure 1 has a complicated structure in which a cavity is present under the second photosensitive film 22, but can be easily manufactured as described above.

  In addition, after the second exposure step, a third photosensitive film having an absorption in a wavelength band longer than the second wavelength band (λ2) is applied, and a wavelength longer than the second wavelength band (λ2) is applied. A three-dimensional multilayer structure having a three-layer structure can also be produced by developing after exposure with a band.

<Step S16> Heat Treatment The first metal Ti of the first photosensitive film 21 and the second metals Ni and Pd of the second photosensitive film 22 constituting the three-dimensional multilayer structure 1 are both in a complex. Ionic state. Further, the first photosensitive film 21 and the second photosensitive film 22 are in an unstable state having photosensitivity.

  For this reason, as shown in FIG. 2 (F), it is preferable to manufacture the three-dimensional multilayer structure 2 using the three-dimensional multilayer structure 1 as a skeleton.

For example, both metal ions become metal oxides by heat treatment at 300 ° C. for 1 hour. That is, the three-dimensional multilayer structure 2 including the first metal oxide (TiO ₂ ) film 21O and the second metal oxide (NiO, PdO) film 22O is manufactured.

  The thicknesses of the first metal oxide film 21O and the second metal oxide film 22O were both 0.3 μm, which was about 1/10 of the first photosensitive film 21 and the second photosensitive film 22. .

  In the three-dimensional multilayer structure 2, since the metal complex is decomposed and is composed of a metal oxide, it is physically / chemically more stable than the three-dimensional multilayer structure 1.

<Step S17> Reduction Process The three-dimensional multilayer structure 2 was reduced. When a reducing agent such as tetrahydroboric acid (SBH) is used, PdO or the like of the second metal oxide film 22O is reduced to metal Pd to become the second metal film 22M, but the first metal oxide film 21O TiO ₂ is not reduced.

  For this reason, as shown in FIG. 2G and FIG. 5, the three-dimensional multilayer structure 3 is composed of a first metal oxide film 21O and a second metal film 22M.

For example, when the reduction process is performed on the three-dimensional multilayer structure 2 at 200 ° C. for 1 hour in a hydrogen atmosphere, the TiO _{2 of} the first metal oxide film 21O is also reduced to become the first metal film 21M. That is, at least one of the first metal and the second metal may be reduced.

  Further, when the three-dimensional multilayer structure 1 is heat-treated in a hydrogen atmosphere, the metal ions in the complex are reduced directly to the metal. That is, heat treatment and reduction treatment may be performed simultaneously.

  Furthermore, for example, a three-dimensional multilayer structure having a metal sulfide film may be manufactured by performing sulfidation using the three-dimensional multilayer structure 1 as a skeleton. That is, a three-dimensional multilayer structure made of various metal compounds may be produced using the three-dimensional multilayer structure 1 as a skeleton.

<Step S17> Plating As shown in FIG. 2 (H) and FIG. 6, the three-dimensional multilayer structure 3 is immersed in an electroless nickel bath shown below, and a thickness of 3 μm is formed on the second metal film 22M. A nickel plating film was formed to produce a three-dimensional multilayer structure 4. That is, Pd of the second metal film 22M serves as a catalyst for electroless plating.

<Electroless NiP plating bath>
Nickel sulfate hexahydrate 0.10 mol / dm ³
Citric acid 0.20 mol / dm ³
Ammonium chloride 0.75 mol / dm ³
Sodium hypophosphite monohydrate 0.20 mol / dm ³
Thiourea 2.0 mg / dm ³
pH adjuster Sodium hydroxide, sulfuric acid pH: 9.0
Bath temperature: 45 ° C
As described above, according to the manufacturing method of the three-dimensional multilayer structure of the embodiment, the three-dimensional multilayer structure 1 shown in FIG. 2 (E), the three-dimensional multilayer structure 2 shown in FIG. 2 (F), Alternatively, the three-dimensional multilayer structure 3 shown in FIGS. 2 (G) and 5 or the three-dimensional multilayer structure 4 having a large thickness as shown in FIGS. 2 (H) and 6 can be easily manufactured.

  In addition, the manufacturing method of the three-dimensional multilayer structure of this invention is not restricted to embodiment.

  In addition, when the first photosensitive film that is first coated on the substrate receives light in the first wavelength band, it is more resistant to the developer than when light in the second wavelength band that is longer than the first wavelength band is received. A first metal complex whose solubility varies greatly, and a second metal complex whose solubility in the developer changes when the second photosensitive film receives light in the first wavelength band and the second wavelength band. Should be included.

  For this reason, the complex of the first metal and the complex of the second metal may be either a positive complex in which the exposed area is dissolved by the development process, or a negative complex in which the exposed area is polymerized and remains after the development process.

  Examples of the positive complex include metal complexes represented by (Formula 1) or (Formula 2). The metal complex represented by (Formula 1) or (Formula 2) undergoes a photochemical reaction, and the wavelength band of light in which the solubility in a developer changes varies from ligand to ligand. Therefore, among the metal complexes represented by (Formula 1) or (Formula 2), the condition of the complex of the first metal (the solubility in the developer changes when irradiated with light of the first wavelength band) A metal complex satisfying the above requirements, and a metal complex represented by (formula 1) or (formula 2) having a ligand different from that of the first metal complex, Conditions for a bimetallic complex (when the light of the second wavelength band is irradiated, the solubility in the developer changes greatly compared to the case where the first metal complex is irradiated with the light of the second wavelength band) A metal complex satisfying the above is selected.

（式２）

（式１）及び（式２）におけるＭは金属原子である。 (Formula 1)

(Formula 2)

M in (Formula 1) and (Formula 2) is a metal atom.

  X in (Formula 1) is one of the following (d1) to (d10).

(D1) Hydroxide or alkoxide (for example, ethylene glycol, 1,2-hexanediol, catechol derivative, ethoxy group, butoxy group, methoxyethoxy group, cycloten of α-hydroxy ketones, maltol)
(D2) carboxylate (for example, formate, acetate, oxalate, ethylhexanoate)
(D3) β-ketonate (acetylacetonate)
(D4) an organic moiety covalently bonded to the metal (d5) hydrofluoric acid salt, hydrochloride salt, bromosalt, iodate salt (d6) nitrate or nitrite (d7) sulfate or sulfite (d8) perchlorate or Hypochlorite (d9) Phosphate (d10) Borate At least one of R1 to R4 in (Formula 1) and (Formula 2) is any one of (Formula 3) to (Formula 6) It is.

（式４）

（式５）

（式６）

（式３）〜（５）におけるＲ１３は、（式７）又は（式８）である。 (Formula 3)

(Formula 4)

(Formula 5)

(Formula 6)

R13 in (Expression 3) to (5) is (Expression 7) or (Expression 8).

（式８）

（式１）又は（式２）におけるＲ1〜Ｒ4のうち、（式３）〜（式６）のいずれでもないもの、及び（式７）〜（式８）におけるＲ5〜Ｒ8は、それぞれ、下記（ａ１）〜（ａ１４）のうちのいずれかである。 (Formula 7)

(Formula 8)

Among R1 to R4 in (Formula 1) or (Formula 2), those which are not any of (Formula 3) to (Formula 6) and R5 to R8 in (Formula 7) to (Formula 8) are as follows. Any one of (a1) to (a14).

(A1) H
(A2) a saturated or unsaturated alkyl group of C1 to C20, represented by C _n H _{2n +} 1 or _{C n H 2n-1-2x, n} = 1~20, x = range of 0 to n-1 is (a3) alkylamine group (a4) carbinol group (a5) represented by aldehydes or ketones (a6) COOR, R = C m H 2m + 1 or _{C m H 2m-1-2y (m} = 0~ (A7) F, Cl, Br, or I
(A8) CN or NO ₂
(A9) hydroxy or ethers (a10) amines (a11) amides (a12) thio or thioethers (a13) phosphines or phosphoric acids (a14) cyclic groups, benzos, azoles, oxazoles, thiazoles, or dioxols Y in 6) is any one of the following (b1) to (b5).

(B1) F, Cl, Br, or I
(B2) Oxocarbonyl group or CH ₃ COO-
(B3) Amido group or CH ₃ CONH-
(B4) A sulfonyl group or CH ₃ SO _3-
(B5) phosphoryloxy group or Ph ₂ POO—
R9 to R10 in (Expression 7) and R9 to R12 in (Expression 8) are respectively any one of the following (c1) to (c15).

(C1) H
(C2) a saturated or unsaturated alkyl group of C1 to C20, represented by C _n H _{2n + 1} or _{C n H 2n-1-2x, n} = 1~20, x = 0~n-1 of range (c3) represented by carbinol group (c4) an aldehyde or ketone (c5) COOR, R = C m H 2m + 1 or _{C m H 2m-1-2y (m} = 0~20, y = 0 (C6) F, Cl, Br, or I
(C7) CN or NO ₂
(C8) hydroxy or ethers (c9) amines (c10) amides (c11) thio or thioethers (c12) phosphines or phosphoric acids (c13) cyclic groups, benzo, azole, oxazol, thiazole, or dioxol (c14) ) Alkylamine Group (c15) Group Containing 2-Nitrobenzyl Structure Specific positive-type first metal complex and second-metal complex combinations are the same as those described in the embodiment with NBOC-CAT (formula 9) This is a combination of a complex with a first metal (for example, (Formula 11), (Formula 12)) and a complex with NVOC-CAT (Formula 10) and a second metal.

(式１０）

（式１１）

（式１２）

なお、（式１）又は（式２）で表される金属錯体が、露光前は現像液に対し不溶であるが、所定の波長の光を用いた露光により易溶となる理由は以下のように推測できる。（式１）又は（式２）で表される金属錯体は、2-ニトロベンジルアルコール誘導体がエステル結合により結合している構造を有する。この金属錯体は、現像液（特にアルカリ性現像液）に対し不溶である。露光工程において、この金属錯体を含む塗膜に、2-ニトロベンジルアルコール誘導体の部分が吸収するような紫外線を照射すると、エステル結合が切れ、2-ニトロソベンズアルデヒドと、カルボキシカテコール誘導体−金属錯体とが生成する。このカルボキシカテコール誘導体−金属錯体は、エステル結合が切断されて生成したカルボキシル基のために、アルカリ性現像液に易溶となる。よって、（式１）又は（式２）で表される金属錯体は、露光前はアルカリ性現像液に対し不溶であるが、所定の波長の光を用いた露光により易溶となる。 (Formula 9)

(Formula 10)

(Formula 11)

(Formula 12)

In addition, although the metal complex represented by (Formula 1) or (Formula 2) is insoluble in a developing solution before exposure, the reason for being easily soluble by exposure using light of a predetermined wavelength is as follows. Can be guessed. The metal complex represented by (Formula 1) or (Formula 2) has a structure in which a 2-nitrobenzyl alcohol derivative is bound by an ester bond. This metal complex is insoluble in a developer (particularly an alkaline developer). In the exposure process, when the coating film containing this metal complex is irradiated with ultraviolet rays that the 2-nitrobenzyl alcohol derivative portion absorbs, the ester bond is broken, and 2-nitrosobenzaldehyde and carboxycatechol derivative-metal complex are formed. Generate. This carboxycatechol derivative-metal complex is easily soluble in an alkaline developer because of the carboxyl group formed by cleavage of the ester bond. Therefore, the metal complex represented by (Formula 1) or (Formula 2) is insoluble in an alkaline developer before exposure, but becomes readily soluble by exposure using light of a predetermined wavelength.

  Moreover, if the metal complex represented by (Formula 1) or (Formula 2) is used, a high contrast pattern will be obtained. The reason can be estimated as follows. That is, the carboxycatechol derivative-metal complex generated in the exposed part is chemically stable and does not cause insolubilization due to polymerization between the complexes, and therefore has a higher contrast pattern than the conventional complex from which metal hydroxide is released. Easily get. Moreover, if the metal complex represented by (Formula 1) or (Formula 2) is used, a crack is hardly generated in the metal oxide film pattern. In general, the thicker the film thickness, the easier it is for cracks to occur. However, if the metal complex represented by (Formula 1) or (Formula 2) is used, cracks are unlikely to occur, so the film thickness is increased. The reason why cracks hardly occur when the metal complex represented by (Formula 1) or (Formula 2) is used can be estimated as follows. That is, the metal complex represented by (Formula 1) or (Formula 2) has a property that benzene rings are easily stacked between the complexes, so that there is little volume shrinkage in the lateral direction during firing and cracking is difficult to occur. .

  In the metal complex represented by (Formula 1) or (Formula 2), the molar ratio of the ligand to the metal (for example, those represented by (Formula 9) and (Formula 10)) is 0.1-2. A range is preferred. When the molar ratio is 0.1 or more, the contrast of the pattern is further increased. Further, when the molar ratio is 2 or less, the density of the film after the reduction process does not decrease. The molar ratio is particularly preferably 0.5 to 1 or 2.

  Examples of the negative complex used as the complex of the first metal and the complex of the second metal include a metal complex having a β-diketone type molecule as a ligand. As the complex of the first metal and the complex of the second metal, those having a β-diketone structure can be widely used. Specifically, the first metal complex is a complex having acetylacetone (formula 13) as a ligand, and the second metal complex is 1,3-diphenyl-1,3-propanedione (formula 14). The complex is a ligand.

(式１４)

ネガ型錯体は、光化学反応を起こし、現像液に対する溶解性が変化する光の波長が、配位子ごとに異なる。そのため、上記のネガ型錯体の中から、第１金属の錯体の条件（第１波長帯の光を照射したとき、現像液に対する溶解性が変化すること）を満たす金属錯体を適宜選択し、また、上記のネガ型錯体であって、第１金属の錯体とは異なる配位子を有する金属錯体の中から、第２金属の錯体の条件（前記第２波長帯の光を照射したとき、第１金属の錯体に前記第２波長帯の光を照射した場合よりも、現像液に対する溶解性が大きく変化すること）を満たす金属錯体を選択する。 (Formula 13)

(Formula 14)

The negative type complex undergoes a photochemical reaction, and the wavelength of light at which the solubility in the developer changes varies depending on the ligand. Therefore, a metal complex that satisfies the conditions of the first metal complex (the solubility in the developer changes when irradiated with light of the first wavelength band) is appropriately selected from the above negative complex, and In the negative complex, the metal complex having a ligand different from the complex of the first metal, the condition of the complex of the second metal (when the light of the second wavelength band is irradiated, The metal complex satisfying that the solubility in the developer is greatly changed as compared with the case where the first metal complex is irradiated with the light of the second wavelength band is selected.

  Hereinafter, combinations of (first ligand / second ligand) are exemplified. The photo acid generator is a positive type, and the photo radical generator is a negative type.

(式１６)

第１金属及び第２金属としては、次に挙げるいずれかを用いる。Ｂ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｐｏ、Ｓｂ、Ｂｉ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｕ、Ｚｎ、Ｃｄ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｕ。 NBOC-CAT (photo acid generator) / NVOC-CAT (photo acid generator)
NPEC-CAT (photo acid generator) / NPOC-CAT (photo acid generator)
Acetoin (photoradical generator) / naphthoquinonediazide (NQD) ester (photoacid generator) shown in (Formula 15)
Maltol (photo radical generator) / curcumin (photo radical generator) shown in (Formula 16)
Acetylacetone (photo radical generator) / 1,3-diphenyl-1,3-propanedione (photo radical generator)
(Formula 15)

(Formula 16)

Any of the following is used as the first metal and the second metal. B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Po, Sb, Bi, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Au, Zn, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, U.

  In the case where the three-dimensional multilayer structure 4 is manufactured based on the three-dimensional multilayer structure 3, at least one of the first metal and the second metal serves as a catalyst for electroless plating. , Rh, Ni, Pd, Pt, Cu, Ag, or Au.

  The first metal and second metal compounds used to form a complex with the ligand are acetate, methoxide, ethoxide, propoxide, butoxide, acetylacetonate, cyclohexane, which are dissolved in a solvent in which the ligand is dissolved. Pentadiene salt, hydrochloride, carbonate, nitrate, sulfate, phosphate, etc. are used.

  Moreover, you may add various additives to the 1st photosensitive film | membrane 21 and the 2nd photosensitive film | membrane 22 in the range which does not prevent the effect of this invention. Examples of the additive include azobenzene dyes such as benzophenone derivatives, anthraquinone derivatives, coumarin derivatives, benzotriazole derivatives, rhodamine derivatives, and sudan black, which are added for the purpose of increasing the wavelength selectivity of the photochemical reaction. These function as ultraviolet absorbers, quenchers, dissolution inhibitors, and the like.

  As the solvent for the first photosensitive solution and the solvent for the second photosensitive solution, a solvent capable of dissolving the metal complex is used. Specifically, alcohols such as methanol, ethanol and propanol; ketones such as acetone; esters such as ethyl acetate, isobutyl acetate and diethyl malonate; hydroxycarboxylic acid esters such as ethyl lactate; and γ-butyrolactone Lactones, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile, amides such as formamide, N, N-dimethylacetamide, N, N-dimethylformamide, amines such as triethylamine, dimethyl sulfoxide, N-methyl Amino alcohols such as pyrrolidone and 1-aminoethanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, chloroform, benzene, toluene, xylene, water or the like is used.

  Here, the manufacturing method of the coating liquid of the 1st photosensitive metal complex and the coating liquid of the 2nd photosensitive metal complex which can be preferably used in the manufacturing method of the three-dimensional multilayer structure of the embodiment will be described.

  As a coating liquid for the first photosensitive metal complex, (NBOC-Nb) using Nb (niobium) as the first metal, (NBOC-NiPd) using Ni (nickel) and Pd (palladium), Cu (copper) ) (NBOC-Cu) using InSn (indium / sodium), (NBOC-InSn) using Hf (hafnium), (NBOC-Ta) using Ta (tantalum) , (NBOC-Au) using Au (gold) and (NBOC-Co) using Co (cobalt) are synthesized by the following method.

<NBOC-Nb>
NBOC-CAT (4.05 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), pentaethoxyniobium (1.76 mL) is added and heated at 100 ° C. for 1 hour.

<NBOC-NiPd>
NBOC-CAT (1.75 g) and nickel acetate tetrahydrate (1.5 g) were dissolved in ethyl lactate (16 mL) and N, N′-dimethylacetamide (4 mL) at 100 ° C. to obtain “Solution A1”. . NBOC-CAT (0.29 g), 2-methoxyethoxyacetic acid (0.08 mL) and 2-aminoethanol (0.05 g) are dissolved in ethyl lactate (2 mL) and acetone (2 mL), and palladium acetate (0.225 g) is added. Add and dissolve with an ultrasonic cleaner to make “Solution B1”. “Solution A1” and “Solution B1” are mixed.

<NBOC-Cu>
2-Methoxyethoxyacetic acid (0.171 mL) and anhydrous copper acetate (0.272 g) are dissolved in N, N′-dimethylacetamide (2 mL) at 100 ° C. to make “Solution C1”. NBOC-CAT (2.46 g) is dissolved in ethyl lactate (12 mL) and N, N′-dimethylacetamide (2 mL), and tetraisopropoxide titanium (1.04 mL) is added to make “Solution D1”. “Solution C1” and “Solution D1” are mixed and heated at 100 ° C. for 1 hour.

<NBOC-InSn>
NBOC-CAT (5.26 g), methoxyethoxyacetic acid (1.4 mL), indium acetate (5.00 g), tin acetate (0.25 g), and NMP (40 mL) are mixed and heated at 130 ° C for 1 hour Then, remove the acetic acid and NMP with a rotary evaporator (130 ° C for 1 hour), and dry the product with a rotary evaporator (130 ° C for 1 hour) to remove the first photosensitive metal complex (NBOC-InSn). obtain. (NBOC-InSn) is dissolved in ethyl lactate (18 mL) and N, N′-dimethylacetamide (6 mL) by heating at 100 ° C.

<NBOC-Hf>
NBOC-CAT (4.05 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), tetrabutoxyhafnium (2.66 mL) is added, and the mixture is heated at 100 ° C. for 1 hour.

<NBOC-Ta>
NBOC-CAT (4.05 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), pentaethoxytantalum (1.82 mL) is added and heated at 100 ° C. for 1 hour.

<NBOC-Au>
NBOC-CAT (2.03 g) is dissolved in ethyl lactate (12 mL) and N, N′-dimethylacetamide (4 mL), tetraisopropoxide titanium (1.04 mL) is added, and the mixture is heated at 100 ° C. for 1 hour. Add 1 mol / L aqueous sodium chloroaurate solution (0.375 mL).

<NBOC-Co>
NBOC-CAT (7.25 g), 2-methoxyethoxyacetic acid (2.85 mL) and cobalt acetate tetrahydrate (6.24 g) are dissolved in 2-methoxyethanol (82 mL) at 100 ° C.

  Further, as the first photosensitive substance, instead of NBOC-CAT, α-hydroxyketone (1-hydroxycyclohexylphenylketone (HPK), acetoin or maltol) or β-diketone (acetylacetone (AcAc) shown in (Formula 17) is used. ) Etc.) can also be used.

例えば、第１の金属としてＣｕ（銅）を用いた（ＨＰＫ-Ｃｕ）は以下に示す方法で合成される。 (Formula 17)

For example, (HPK-Cu) using Cu (copper) as the first metal is synthesized by the following method.

<HPK-Cu>
2-Methoxyethoxyacetic acid (0.171 mL) and anhydrous copper acetate (0.272 g) are dissolved in N, N′-dimethylacetamide (2 mL) at 100 ° C. to make “Solution C1”. HPK (1.74 g) is dissolved in ethyl lactate (12 mL) and N, N′-dimethylacetamide (2 mL), and tetraisopropoxide titanium (1.04 mL) is added to form “solution E1”. “Solution C1” and “Solution E1” are mixed and heated at 100 ° C. for 1 hour.

  As a coating solution for the second photosensitive metal complex, (NVOC-Ti) using Ti (titanium) as the first metal, (NVOC-Nb) using Nb (niobium), Ni (nickel) and Pd (palladium) (NVOC-NiPd) using Cu, (NVOC-Cu) using Cu (copper), (NVOC-InSn) using InSn (indium / soot), (NVOC-Hf) using Hf (hafnium) (NVOC-Ta) using Ta (tantalum), (NVOC-Au) using Au (gold), and (NBOC-Co) using Co (cobalt) are synthesized by the following method.

<NVOC-Ti>
NVOC-CAT (4.89 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), tetraisopropoxide titanium (2.07 mL) is added, and the mixture is heated at 100 ° C. for 1 hour. .

<NVOC-Nb>
NVOC-CAT (4.89 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), pentaethoxyniobium (1.76 mL) is added and heated at 100 ° C. for 1 hour.

<NVOC-NiPd>
NVOC-CAT (2.10 g) and nickel acetate tetrahydrate (1.5 g) are dissolved in ethyl lactate (16 mL) and N, N′-dimethylacetamide (4 mL) at 100 ° C. to obtain “Solution A2”. . NVOC-CAT (0.35 g), 2-methoxyethoxyacetic acid (0.08 mL) and 2-aminoethanol (0.05 g) were dissolved in ethyl lactate (2 mL) and acetone (2 mL), and palladium acetate (0.225 g) was added. Add and dissolve with an ultrasonic cleaner to make “Solution B2”. “Solution A2” and “Solution B2” are mixed.

<NVOC-Cu>
2-Methoxyethoxyacetic acid (0.171 mL) and anhydrous copper acetate (0.272 g) are dissolved in N, N′-dimethylacetamide (2 mL) at 100 ° C. to make “Solution C2”. NVOC-CAT (2.97 g) is dissolved in ethyl lactate (12 mL) and N, N′-dimethylacetamide (2 mL), and tetraisopropoxide titanium (1.04 mL) is added to make “Solution D2”. “Solution C2” and “Solution D2” are mixed and heated at 100 ° C. for 1 hour.

<NVOC-InSn>
NVOC-CAT (6.32 g), methoxyethoxyacetic acid (1.4 mL), indium acetate (5.00 g), tin acetate (0.25 g), and NMP (40 mL) were mixed and heated at 130 ° C for 1 hour. After that, acetic acid and NMP are removed with a rotary evaporator (130 ° C., 1 hour), and the product is further dried with a rotary evaporator (130 ° C., 1 hour). (NVOC-InSn) is dissolved in ethyl lactate (18 mL) and N, N′-dimethylacetamide (6 mL) at 100 ° C.

<NVOC-Hf>
NVOC-CAT (4.89 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), tetrabutoxyhafnium (2.66 mL) is added, and the mixture is heated at 100 ° C. for 1 hour.

<NVOC-Ta>
NVOC-CAT (4.89 g) is dissolved in ethyl lactate (15 mL) and N, N′-dimethylacetamide (10 mL), pentaethoxytantalum (1.82 mL) is added, and the mixture is heated at 100 ° C. for 1 hour.

<NVOC-Au>
NVOC-CAT (2.45 g) was dissolved in ethyl lactate (12 mL) and N, N′-dimethylacetamide (4 mL), tetraisopropoxide titanium (1.04 mL) was added, and the mixture was heated at 100 ° C. for 1 hour. Add 1 mol / L aqueous sodium chloroaurate solution (0.375 mL).

<NVOC-Co>
NVOC-CAT (8.80 g), 2-methoxyethoxyacetic acid (2.85 mL) and cobalt acetate tetrahydrate (6.24 g) are dissolved in 2-methoxyethanol (82 mL) at 100 ° C.

  Moreover, the coating liquid of (NQD-Cu) which used naphthoquinone diazide (NQD) ester as a 2nd photosensitive substance instead of NVOC-CAT and used Cu (copper) as a 1st metal is shown below. Synthesized by the method.

<NQD-Cu>
2-Methoxyethoxyacetic acid (0.171 mL) and anhydrous copper acetate (0.272 g) are dissolved in N, N′-dimethylacetamide (2 mL) at 100 ° C. to make “Solution C2”. Dissolve ethyl protocatechuic acid (1.55 g) in ethyl lactate (12.5 mL) and N, N′-dimethylacetamide (2 mL), add tetraisopropoxide titanium (1.04 mL) to make “Solution E1”. . “Solution C1” and “Solution E1” are mixed and NQD ester (0.75 g) is added to the solution heated at 100 ° C. for 1 hour.

  In the first exposure process and the second exposure process, as a light source, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a halogen lamp or the like, an excimer laser, a fundamental wavelength of a Nd-YAG laser, a secondary, tertiary, or fourth A laser of the next harmonic, a fluorescent lamp such as a black light or a sterilizing lamp, a light emitting diode, or sunlight is used.

  When a lamp is used as the light source, the light in the second wavelength band is obtained by cutting the light in the first wavelength band from the light of the lamp using an arbitrary sharp cut filter, bandpass filter, interference filter, or spectrometer. As the light including the first wavelength band, all the light from the lamp may be used, or a component overlapping the second wavelength band may be cut from the total light from the lamp by the above method.

  When a laser is used as the light source, a laser having an oscillation wavelength (wavelength including the first wavelength band) preferentially absorbed by the first metal complex and an oscillation preferentially absorbed by the second metal complex A laser having a wavelength (a wavelength including the second wavelength band) is used in combination.

  In the development process, development is performed using a developer. The developer is appropriately selected according to the type of the first metal complex and the second metal complex. As the developer, for example, an alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution having a predetermined concentration, an acid aqueous solution such as an acetic acid aqueous solution, or an organic solvent such as ethanol, 2-propanol, or acetone is used.

  In the heat treatment step, for example, baking is performed using a hot plate, a muffle furnace, a roller conveyance furnace, or the like. Moreover, you may irradiate electromagnetic waves, such as infrared heating and laser irradiation.

  In the reduction step, it is preferable to use a solution containing hypophosphorous acid, hydrazine, borohydride, dimethylamine borane, tetrahydroboric acid (SBH), aminoborane (DMAB) and the like.

  In the electroless plating step, a desired metal film / alloy film can be formed by selecting an electroless plating bath according to the purpose. For example, an electroless plating film made of In, Sn, Pb, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, or the like is desired. The film is formed to a thickness of.

  For example, for example, the following electroless gold plating bath is excellent in stability and can be particularly preferably used in the present invention.

<Electroless Au plating bath>
Sodium chloroaurate dihydrate 0.01 mol / dm ³
Citric acid 0.25 mol / dm ³
6-aminopenicillanic acid 0.05 mol / dm ³
Ascorbic acid 0.20 mol / dm ³
Pentaethylenhexamine 0.01 mol / dm ³
2,2'-bipyridyl 100ppm
PEG200 100ppm
pH adjuster Potassium hydroxide pH: 12.0
Bath temperature: 70 ° C
When only the second metal is an electroless plating catalyst as in the embodiment, an electroless plating film is formed only on the second metal. On the other hand, when only the first metal is an electroless plating catalyst, an electroless plating film is formed only on the first metal. When the first metal and the second metal are electroless plating catalysts, an electroless plating film is formed on the first metal and the second metal.

  The present invention is not limited to the above-described embodiments, and various changes and modifications can be made without departing from the scope of the present invention.

Claims (4)

When the substrate receives light in the first wavelength band, the first metal complex whose solubility in the developer changes greatly compared to when light in the second wavelength band having a longer wavelength than the first wavelength band is received. A first application step of coating a first photosensitive film including:
A first exposure step of pattern-exposing the first photosensitive film with light including the first wavelength band;
A second photosensitive film containing a second metal complex whose solubility in the developer changes when receiving light in the first wavelength band and the second wavelength band is coated on the first photosensitive film. A second coating step,
A second exposure step of pattern-exposing the second photosensitive film with light including the second wavelength band and not including the first wavelength band;
And a developing step of developing the first photosensitive film and the second photosensitive film using the developer. A method for producing a three-dimensional multilayer structure. The complex of the first metal is represented by (Formula 1),
The method for producing a three-dimensional multilayer structure according to claim 1, wherein the complex of the second metal is represented by (Formula 2).
(Formula 1)

(Formula 2)

M in (Formula 1) and (Formula 2) is a metal atom.
X in (Formula 1) is one of the following (d1) to (d10).
(D1) hydroxide or alkoxide (d2) carboxylate (d3) β-ketonate acetylacetonate (d4) organic moiety covalently bonded to metal (d5) hydrofluoric acid salt, hydrochloride salt, bromosalt d6) nitrate or nitrite (d7) sulfate or sulfite (d8) perchlorate or hypochlorite (d9) phosphate (d10) borate R1 in (formula 1) and (formula 2) At least one of -R4 is any one of (Formula 3)-(Formula 6).
(Formula 3)

(Formula 4)

(Formula 5)

(Formula 6)

R13 in (Formula 3) to (Formula 5) is (Formula 7) or (Formula 8).
(Formula 7)

(Formula 8)

Among R1 to R4 in (Formula 1) or (Formula 2), those which are not any of (Formula 3) to (Formula 6) and R5 to R8 in (Formula 7) to (Formula 8) are as follows. Any one of (a1) to (a14).
(A1) H
(A2) a saturated or unsaturated alkyl group of C1 to C20, represented by C _n H _{2n +} 1 or _{C n H 2n-1-2x, n} = 1~20, x = range of 0 to n-1 is (a3) alkylamine group (a4) carbinol group (a5) represented by aldehydes or ketones (a6) COOR, R = C m H 2m + 1 or _{C m H 2m-1-2y (m} = 0~ (A7) F, Cl, Br, or I
(A8) CN or NO ₂
(A9) hydroxy or ethers (a10) amines (a11) amides (a12) thio or thioethers (a13) phosphines or phosphoric acids (a14) cyclic groups, benzos, azoles, oxazoles, thiazoles, or dioxols Y in 6) is any one of the following (b1) to (b5).
(B1) F, Cl, Br, or I
(B2) Oxocarbonyl group or CH ₃ COO-
(B3) Amido group or CH ₃ CONH-
(B4) A sulfonyl group or CH ₃ SO _3-
(B5) phosphoryloxy group or Ph ₂ POO—
R9 to R10 in (Expression 7) and R9 to R12 in (Expression 8) are respectively any one of the following (c1) to (c15).
(C1) H
(C2) a saturated or unsaturated alkyl group of C1 to C20, represented by C _n H _{2n + 1} or _{C n H 2n-1-2x, n} = 1~20, x = 0~n-1 of range (c3) represented by carbinol group (c4) an aldehyde or ketone (c5) COOR, R = C m H 2m + 1 or _{C m H 2m-1-2y (m} = 0~20, y = 0 (C6) F, Cl, Br, or I
(C7) CN or NO ₂
(C8) hydroxy or ethers (c9) amines (c10) amides (c11) thio or thioethers (c12) phosphines or phosphoric acids (c13) cyclic groups, benzo, azole, oxazol, thiazole, or dioxol (c14) ) Alkylamine group (c15) Group containing 2-nitrobenzyl structure   The first metal complex is a complex of 4- (2-nitrobenzyloxycarbonyl) catechol ligand and the first metal, and the second metal complex is 4- (4,5-dimethoxy- The method for producing a three-dimensional multilayer structure according to claim 2, which is a complex of a 2-nitrobenzyloxycarbonyl) catechol ligand and the second metal. At least one of the first metal and the second metal is a metal that serves as a catalyst for electroless plating reaction,
After the development step, a reduction step of reducing metal ions serving as a catalyst for the electroless plating reaction to metal,
The method for producing a three-dimensional multilayer structure according to claim 3, further comprising a plating step of forming an electroless plating film.

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