JPS61198634A - Manufacture of semiconductor device - Google Patents

Abstract

PURPOSE:To improve the adhesion when turning into an insulation film on a later heat treatment, by a method wherein organoleptic dialcoxysilane is used as the adhesion modifier in formation of a layer made of photo-sensitive heat-resistant polymer precursor on the semiconductor surface or on an organic insulation film formed over the surface. CONSTITUTION:In formation of a layer made of photo-sensitive heat-resistant polymer precursor on the semiconductor surface or on the surface of an organic insulation film formed over the surface, organoleptic dialcoxysilane expressed by Formula is used as the adhesion modifier. As the organoleptic dialcoxysilane, a dialcoxy type silane series coupler, particularly, such as gamma- aminopropylmethyldimetoxysilane, N-beta(aminoethyl), gamma-aminopropyldimetoxysilane, gamma-glycidoxypropylmethyldimetoxysilane, or gamma- mercaptopropylmethyldimetoxysilane, is excellent.

Description

[Detailed Description of the Invention] [Industrial Application] The present invention is directed to improving the adhesion when forming a heat-resistant polymer film on the surface of a semiconductor device using a photosensitive heat-resistant polymer precursor. The present invention relates to a semiconductor device and a method for manufacturing the same.

[Prior art]

Conventionally, photosensitive heat-resistant polymer precursors have been used to protect the surfaces of semiconductor devices and provide interlayer insulation between solid-state devices.

For example, it is possible to protect the surface of a semiconductor where two regions with different semiconducting properties are joined and the exposed part of a p-n junction, or to protect the exposed part of a semiconductor substrate that has at least one semiconductor element. An inorganic insulating film such as silicon nitride is formed, a photosensitive heat-resistant polymer precursor layer is provided on top of the inorganic insulating film, and the layer is irradiated with light through a photomask and developed to form a via hole. The layer is then heat-treated to make it highly insulating, and a conductor circuit is formed on the surface of the layer and electrically connected to the underlying circuit through six ear holes. A heat-resistant polymer precursor is used as an insulating film for multilayer wiring.

When a heat-resistant polymer film is formed using a 1 photosensitive heat-resistant polymer precursor in this way, it is possible to form micro-diameter via holes with high precision and efficiently form a multilayer wiring board with excellent 1+ flatness. can.

However, when forming an insulating film for multi-layer wiring, when applying a photosensitive heat-resistant polymer precursor to St or an inorganic insulating film, coating defects may cause cabin holes, or the current pressure relief after exposure. Partial peeling of the pattern may occur due to the liquid, which is undesirable. In particular, in the case of a photosensitive heat-resistant polymer precursor, when it is chemically changed into a heat-resistant polymer film through high-temperature heat treatment 12, the curing strain and thermal strain during the heat treatment are extremely large, so it cannot be used with SI or inorganic insulating films. Reliability was not sufficient because adhesion failure occurred at the interface of the polymeric insulating film, and moisture entered the interface, resulting in deterioration of characteristics.

As a method for improving these drawbacks, Si-? It has been proposed to interpose an organic silicon compound at the interface between an inorganic insulating film and a heat-resistant polymer film. For example,
No. 207, Tokukai Sho! ? -23vj publication uses trialkoxy-type silane coupling agents such as vinyl, epoxy, and methacryloquine, which are applied to the surface of Si or inorganic insulating films, and are mixed in advance into a photosensitive heat-resistant resin. A method is disclosed. Also, Tokukai Akihiro-/Hiroshi! No. 7 Rihiro Publication discloses a method using an organosilicon compound aluminum chelate. Although these disclosed examples state that adhesion is improved by using common organosilicon compounds, not all organosilicon compounds improve adhesion in this system. do not have. Trialkoxy-type vinyl-based and epoxy-based silane coupling agents improve coating properties, but the adhesion between the imide film and SI or inorganic insulating film after heat treatment is insufficient, and methacryloxy-based silane coupling agents may cause coating defects. However, it has the disadvantage that a uniform coating film cannot be obtained.

Further, although the coating properties and adhesion of trialkoxy-type amine-based sila/coupling agents are somewhat improved compared to the above-mentioned sila/coupling agents, they are not sufficient and are not satisfactory.

[Problem that the invention seeks to solve]

The present invention solves the above-mentioned drawbacks and improves the coating properties and adhesion when forming a layer of a photosensitive heat-resistant polymer precursor on the surface of a semiconductor or the surface of an inorganic insulating film formed on the surface. The present invention provides a new method for manufacturing a semiconductor device, which improves the adhesion of an insulating film through subsequent heat treatment.

[Means for Solving the Problems] That is, the present invention provides a method for forming a layer made of a photosensitive heat-resistant polymer precursor on the surface of a semiconductor or the surface of an inorganic insulating film formed on the surface. In particular, the present invention relates to a method for manufacturing a semiconductor device, characterized in that a functional dialkoxysilane is used as an adhesion improver.

The present invention will be explained in detail below.

The semiconductor device used in the present invention includes a single diode,
An integrated circuit consisting of a single transistor or a combination of diodes, transistors/sisters, and passive elements (resistors, capacitors, etc.). It is the surface of a semiconductor, or Sl, or a passive element. Furthermore, the term "on the surface of the inorganic insulating film formed on the surface of the semiconductor device" refers to the surface of the insulating film formed on the surface of the semiconductor device, such as silicon nitride, silicon nitride, phosphosilicate glass, etc. It is something.

The functional dialkoxy 7-rane used in the present invention has the general formula %) [In the formula, A has 7 to 10 carbon atoms and has a vinyl group, an epoquine group, a methacrylic group, an amino group, or a mercapto group at the end. a group having at least one organic functional group selected from R1 represents an alkyl group having 1 to 3 carbon atoms; < is γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyldimethoxysilane, γ-glindoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxy7ran, etc. These dialkoxy type silane coupling agents are excellent in achieving the objects of the present invention.

The functional dialkoxy/silane can be applied onto the surface of the semiconductor device, an inorganic surface formed on the surface, or a combination thereof, or mixed with a photosensitive heat-resistant polymer precursor. Good too.

Although there are no particular limitations on the coating method for the functional dialkoxy 7-ran, it is preferable to dissolve it in an appropriate solvent and apply it using a spinner.

It is preferable that the thin film of functional dialcoquinane is formed as uniformly and thinly as possible within the range of effective adhesion.

Generally, a single mixed solvent of organic solvents such as water and alcohol is dissolved in a concentration of lCo,ooi to 3 weight by weight and coated by spin coating. At a concentration of 0.00/wt% or less, the adhesion is poor, and at a concentration of 3 wt% or more, the adhesion is sufficient, but
Unsuitable due to economic considerations.

After spin coating, dry at room temperature. It may be heat-treated and dried if necessary. Dry at room temperature! Preferably, the reaction is carried out at a suitable temperature between 0° C. and 30 minutes.

When a functional dialkoxydine run is mixed into a photosensitive heat-resistant polymer precursor, 0.0! −j
It is advantageous to add % by weight, preferably o, i-2% by weight. 0.0! If the weight is less than 5% by weight, the adhesion will be poor, and if it is more than 5% by weight, the storage stability will be poor when the photosensitive heat-resistant polymer precursor is made into a solution, which is inappropriate.

The photosensitive heat-resistant polymer precursor used in the present invention is a polymer having a repeating unit represented by the general formula.

[In the formula, For the polymer represented by the formula [old] Specifically, X in the formula is 3 or a valent carbocyclic group or a heterocyclic group, and examples of such X include a fused polycyclic aromatic group such as a benzene ring, a naphthalene ring, and anthraceyel. Examples include rings, heterocyclic groups such as pyridine and thiophene, and groups represented by the general formula (L]λ2X2 is CHI t or CF3). Among these, carbonate,
Furthermore, those represented by the formula O (q is O or l) (It) [I[s) are preferred.

Y in the general formula (11) K is λ, 3, or a divalent carbocyclic group. Several tens to 1 g of divalent aromatic hydrocarbon ring,
A heterocyclic group derived from pyridine, imidazole, etc. and the formula (14) [j[s] [Yl in the formula is ET % CH3, CCHs)! C
Hs OCH3, C0OH, H3 -C)1=CH-, -〇-1-s-1-C-18-Q'
T11 ゝY, and N4 are Hs CHs% C2H5s 0CH
s, halogen atom, C0OH%So, )It or NO
□, N5 and 1 are HSCN, halogen atom, CM
, 0CHs, So, H-spanning OH], and the like. Among these, carbon number io~/lI
divalent aromatic hydrocarbon ring, N2 is +CHt+ (
However, pFio or l), -C-1P
A group represented by the formula [X] in which I+-SO-1-0-Makake-S- and N3 and N4 are both hydrogen atoms is preferred, and a group represented by the formula is also preferred.

W in the above general formula [ta] is converted to TtOH by heat treatment.
(R has the same meaning as above),
A group capable of forming a ring by reacting with the carbonyl group of -COOR, and as such a group, especially K -CMHz
is suitable. Moreover, as n, it is preferable.

The polymer used in the present invention is a compound represented by the general formula and a compound represented by the general formula Z2 Y Z2 ...
It can be obtained by polycondensation or polyaddition with the compound represented by I). Examples of zI in the general formula [v] are a, C0OH(Vt), Co CI CV2
), -NCO(Vs), -NHZ (N4), Of
((Vs), and the corresponding general formula [v] abbreviation is shown within 0. Also, the general formula C'Q]K
Examples and examples are -COCI (VI+), C00H (
N12), NCOCVIa], and NHz [:V14), and the abbreviations of the corresponding general formulas [■] are shown within 0. In addition, X, R.

Y and W have the same meanings as above.

By polycondensation or polyaddition reaction between the compound represented by the general formula [v] and the compound represented by the general formula symbol, Zl
and z2 react to form bonded chain 2.

In this case, preferred combinations of Z and 22, the 20 types produced, and the term structure names produced when the resulting nonapolymer is heat-treated are shown in Table 1.

(Leaving space below) Table 1 [Note] *1 III structure ■M: Imide ring QD: Quinazolinedio/11 OD= OxazinedioyJl In addition, the combination of numbers l and λ in Table 1, W
When is CO2, an isoindoroquinazolinedione ring is formed by the heat treatment, and those having this structure are preferred because they exhibit particularly high heat resistance.

Moreover, the polymer of formula [■] can also be produced by the method shown below. That is, the compound represented by the general formula (Vls)i or [■4
The carboxyl group of the product obtained by reacting with the compound represented by ] is reacted with an epoxy compound represented by the general formula % (R in the formula has the same meaning as the subscript) 9, The polymer was obtained. Preferred combinations and reaction formulas for this reaction are shown in formulas CV&), [:■Yuki] and [■3].

(Left below) ≠ drunk↑ ■匡0 ++
1 ■ Mochi T ↑ 10 Toomi The compound represented by the above general formula CV+1 can be obtained, for example, by ring-opening the anhydride represented by the general formula [v6] with ROH (R has the same meaning as above). . Nucleic acid anhydride [v
6], for example, anhydrous pyromellitic acid, 3.3',
ψ, ≠′-benzophenone tetracarbo/acid dianhydride,
313', ψ, v'-diphenyl ether tetracarboxylic dianhydride, 3.3', ψ, ψ'-diphenyltetracarboxylic dianhydride, 3.3', ≠+v'-diphenylsulfone dianhydride , λ, j, i7-naphthalenetetracarboxylic anhydride, thiophene-2゜J
, u, j-tetracarboxylic anhydride, ! +, 2-bis (
Examples of the alcohol ROM include allyl alcohol, crotyl alcohol, cheraniol, nerol, citronellol, perillyl alcohol, and hydroquine methylstyrene alcohol. When these fermented anhydrides [■] are reacted with alcohol ROM, the reaction is accelerated by adding pyridino, methylaminopyridine, or the like.

The combination of numbers l and λ in Table 1 above is an example of a preferred embodiment, and the diamine represented by the general formula [■4] used in this combination is, for example, u
, <z'-diaminodiphenyl ether, '4. tl'
-diaminobiphenyl 1.2. ni-diaminotoluene,
Hiro, Hiro I-diaminobenzophenone, ≠, l'-diaminodiphenylsulfone, phenylinodane diamine, 4
<, <z'-diaminodiphenylsulfo, p-7 22-diamine, m-7 22-diamine, /, j-diaminonaphthale, 3.3'-dimethoxy7-v, ≠I-diaminobiphenyl , 3.3'-dimethyl, -44,@/-
Diaminobiphenyl, 0-toluidine sulfo/,! ,λ
-Bis(Hiro-aminophenoxephenyl)propane, Bis(Hiro-aminophenoxyphenyl)sulfone, Bis(Hiro-aminophenoxyphenyl)propane,
quaaminophenoxyphenyl) sulfide, /, F-
Bis(guaminophenoquine)be/dan,/, 3-bis(guaminophenoxy)penzea, 3. u'-diaminodiphenyl ether, Wauterbis(tI-aminophenyl)anthracene-(10), Ri, Terbis(Hiro-
amino-nyl)fluorene, 3,3'-diaminodiphenyl sulfo/, ≠, ≠'-di(3-aminophenoquine)) phenyl sulfone, F+v'-diaminobenzanilide, J, 4''-diaminodiphenyl ether, p, a
'-CI, 3-phenylenebisCl-1-1-ruethylene)],! , @'-(/, gouphenylenebis(/-
methylethylidene)), a, R'-(m-phenylene diisopropylide/)bis(m-toluidine), ≠ slag'
-(p-phenylenediisopropylidene)bis(m-toluidi/) and the like.

Furthermore, R in the general formula CU]K is a group having a carbon-carbon double bond, such as -R'-C
H=CH-R' (IVs)
HIN + CH-C=CT(2)nCPi*] ■ R' [In the formula, R' is hydrogen or a methyl group, R# is the number of carbon atoms 1 to
The alkyl group or oxyalkyl JLn of 3 is /~3,
l represents J-n respectively].

As an example of [■1], CHt　OCCH=CH2 ! 1 0 CH.

As an example of [■2], -CHI OCCH=CH2 As an example of [■3], −CHt(ΣCH=CHt -CHz CHt uC) I=CHz -CH20-1f))-CH=CH2 As an example of [■4], As an example of (■s:], CH2CH=CH2 -CH2CHz-CH=CH2 As an example of [■6] As an example of [■7] As an example of [corner], As an example of [■,], NH2CH2C)I=CI(2 Book 2 CH2-C=CHt disorder Examples include.

A sensitizer having an ultraviolet absorption peak wavelength of 300 K, such as Michler's ketone, is added to the photosensitive heat-resistant polymer precursor, and the mixture is dissolved in a solvent such as dimethylformamide or N-methylpyrrolidone. The photosensitive heat-resistant polymer precursor solution is applied onto a surface on which a thin film of functional dialkoxysilane has been previously formed, or by adding functional dialkoxysilane to the solution. As a coating method, a coating machine such as a spin coater, a roll coater 1, or a screen printer is used. Thereafter, the solvent is dried using a hot air dryer, hot grate, etc. to form a coating film. Next, using a photomask, the areas where the heat-resistant polymer layer is needed are irradiated with ultraviolet rays to harden them.

Next, remove the unexposed areas with a developer such as γ-butyrolactone or N-methylpyrrolid or a rinse solution such as isopropyl alcohol or xylene to form a pattern.
An insulating layer with excellent heat resistance is formed by heat treatment at 0-170°C.

〔Effect of the invention〕

The heat-resistant insulating layer formed in this way has excellent adhesive properties,
The moisture resistance and electrical properties of the semiconductor device can be further improved. Furthermore, since the chemical resistance is improved, application to wet processes becomes possible.

[Example] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these in any way.

Adhesion evaluation of the photosensitive heat-resistant polymer precursor was performed by the Sellotape peeling method described below.

(1) Heat treat the adherend at 300° C. for 30 minutes, and cool to room temperature in a desiccator.

(2) 0.0% of the functional dialkoxylan. /% solution is applied to the adherend using a spin coater.

(Condition: rooorra -30 seconds) Poke and air dry at room temperature for 3 to IQ minutes.

(3) Apply a solution of a photosensitive heat-resistant polymer precursor to the adherend using a spin coater.

(Condition: tooor%-2Q seconds) Subsequently, it is dried for 20 minutes at 70°C using a hot air dryer.

(4) -The white square with side /+111 is /IEII
io at intervals.

Place the photomasks lined up in a side stop square in close contact, and 2jt
Mask aligner (exposure machine) equipped with OW ultra-high pressure water lamp
was used for 2 minutes of exposure.

(δ) After being immersed in a developer of T-butyrolactone/isopropyl alcohol (777 volume ratio) for 60 seconds and running, it was rinsed with inopropyl alcohol to form 100 /15+ square resin layers.

(6) Ktl for 1 hour at 200°C under N atmosphere
A cured film is formed by heat treatment at θO°C for 7 hours.

(γ) The adherend on which the cured film has been formed is immersed in boiling water at 100°C for 6 hours.

(8) Take out the adherend, immerse it in ethanol for several minutes, and then air dry it.

(9) Apply mending tape made by Sumitomo 3M,
Peel off at a speed of /♂θ degree inward direction O■/min. 1III
Let the number of bumps in which more than % of the squares of I do not peel off be X,
Display adhesion with x7ioo. Adhesion is 100//Q
0 is the best and 0/100 is the worst.

In addition, the chemical resistance evaluation is similar to the adhesion evaluation, with K(1) to (
The adherend on which the cured film was formed by method 6) was immersed in a predetermined chemical L% (81 to 9), and the adhesion after immersion was evaluated.

Example of a spear / Pyromellitic dianhydride u in 31 separable flasks
3.1. y, 2-hydroxyethyl methacrylate) j
r, /ml, γ-butyrolactone 7uO- and viridi //θjsl! was added and stirred at room temperature for 20 hours.

To this solution was added dropwise thionyl chloride jOf over 1 hour under water cooling, and the solution was stirred at room temperature for 2 hours. This solution Ku, t(′-diaminodiphenyl ether 3 /,
A mixture of IP and 73jOwd of γ-butyrolact was added and stirred for 2 hours. Furthermore, 1/ml of ethanol was added and stirred for 70 hours. Then, γ-7 tyrolactone to
When □- was added and slowly poured into 101 water, a thread-like solid was precipitated. After washing well by changing the water several times, filtration, and thorough washing with ethanol and water, vacuum drying was performed. This powder polymer! ! f1 Michler's Katone lj1 was dissolved in 33fK of N-methylpyrrolidone to obtain a polymer solution C-/.

Reference example! Synthesis was carried out in the same manner as in Reference Example 1, except that 1 p/)゛phenonetetracarboxylic dianhydride≦g, g1 was used instead of pyromellitic dianhydride.

This powder polymer iff, Michler's ketone/I
F was dissolved in N-methylpyrrolidone 3reK to obtain a polymer solution C-1.

Reference Example 3 An amine solution was prepared by dissolving 1 ioy of diaminodiphenyl ether in N-methylpyrrolidone 2909 and running. Dissolve pyromellitic dianhydride/20f in dimethylacetamide 3101 K, then N-methylpyrrolidone/1
01 was added and dissolved to prepare a Shun solution. , 31 using a separable flask, 60°C amine solution Kll! A polymer solution was obtained by adding the solution and reacting for 3 hours. This polymer solution j0t1 Michler's ketone/, 2f
3Of N-methyl birolide 7ffR solution L7Ir solution and dimethylaminoethyl methacrylate 10. f'kN-methylpyrrolidone IOf Ic dissolution 1. The obtained solutions were mixed to obtain a polymer solution C-j.

Reference Example Synthesis was performed in the same manner as in Reference Example 3 except for using K and benzopheno/tetracarboxylic dianhydride 1772 instead of gpyromellitic dianhydride. This polymer solution rot, a solution of Michler's ketone/, -2 dissolved in 309ON-methylpyrrolidone, and a solution of dimethylaminoethyl methacrylate 7θ, -2 dissolved in N-methylpyrrolidone 10f/ were mixed, and the polymer solution C-≠ And so.

Example 1 After forming a transistor, a protective film of silicon oxide was formed on the entire surface of the adhesive film, and γ-glycidoxyglobylmethyldimethoxane was applied to it according to the conditions of adhesion evaluation using the sellotape peeling method described in the article. Forming a film 1-1
Next, a 1° polymer film was formed using the C-/polymer solution of Reference Example 1. Subsequently, a fog light treatment, a heat treatment, and a heat treatment were performed to form a cured film (thickness: 70 μm). Next, adhesion was evaluated by the sellotape peeling method described in 1 above, and the result was 10/100.

Example 1 - As a functional dialkoxysilane, γ-aminopropylmethyldimethoxysilane/, N-β(aminoethyl)-γ
1. In the same manner as in Example 1, using 7-minopropyl methyl dimethoxine silane and γ-mercaptogropyl methyl dimethoxysilane. Adhesion was evaluated. The results are shown in Table/.

Table / Comparative Example /-1 In the same manner as in Example /, vinyltriethquine 7rane, γ-glycidoxy/probyltrimethoxy/silane, and γ-aminobrobyltriethquinolane were used as functional dialkoxysilanes. without using organosilicon compounds,
A product with a directly cured film was also produced at the same time, and adhesion was evaluated.

(In addition, if an organosilicon compound is not used, C-/
When forming a film using this polymer solution, repellency was observed and a film of uniform thickness could not be obtained. ) The results are shown in Table 2.

Table 2 Example j~/6 C-, 2~C-ψ of Reference Example 2~μ in the same manner as Example/
Adhesion was evaluated using the polymer solution of Example 1-ψ and the functional dialkoxysilane of Example 1-ψ. The results are shown in Table 3.

(Left below) Table 3 Example 77~O Example! Table tA1/(shows the results when the immersion time in boiling water was changed for -Female).

Example +21N Co3 Adhesion was evaluated in the same manner as in Example 1 using a mixture of the C-2 polymer of Reference Example 2 and two functional dialkoxysilanes in a ratio of 1:1. Show your results! Shown below.

table ! Examples, 21 to λ7 In order to evaluate the adhesion to the adherend, Example 2 and a Noricon wafer with thin films of silicon oxide, silicon nitride, and aluminum formed on the entire surface were used. Adhesion was evaluated in the same manner. The results are shown in Table 6.

(Margins below) Table B Example λg~31 The chemical resistance of phosphoric acid-based and 7-acid-based chemicals was evaluated for samples prepared in the same manner as in Examples j-t. The results are shown in Table 7.

Table 7 Temperature to °C Immersion time 30 minutes x) PTS hydrofluoric acid water: qO% ammonium fluoride aqueous solution = i:i.

Temperature -1℃　Immersion time 10 minutes

Claims (2)

[Claims] (1) When forming a layer consisting of a photosensitive heat-resistant polymer precursor on the surface of a semiconductor or the surface of an inorganic insulating film formed on the surface, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼......[I] ▲Mathematical formulas, chemical formulas, tables, etc. a group having at least one organic functional group, R_
1 represents an alkyl group having 1 to 3 carbon atoms] A method for manufacturing a semiconductor device, characterized in that a functional dialkoxysilane represented by the following formula is used as an adhesiveness improver. (2) The photosensitive heat-resistant polymer precursor has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...... [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X and Y are (2+n)-valent carbocyclic or heterocyclic groups, Z is ▲There are numerical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R is carbon-
A group having a carbon double bond, W is a group capable of reacting with the carbonyl group of -COOR by heat treatment to form a ring, n is 1 or 2, m is 0, 1 or 2, and COOR and Z are mutually The method according to claim 1, which is a polymer having a repeating unit represented by the following formula: in an ortho-position or peri-position relationship.