KR20010028956A - Polyphenylene oligomers, processes for coating such oligomers, and articles comprising the cured reaction product of such oligomers - Google Patents

Abstract

PURPOSE: A polyphenylene oligomer composition, a method for preparing an integrated circuit and a coated product from the composition, and an integrated circuit product are provided, which composition has a capability for filling gaps and for flattening a patterned surface, needs a small amount of dispense volume, and is useful as an interlayer dielectric in an integrated circuit. CONSTITUTION: The composition comprises a curable oligomer:£A|w£B|z£EG|v (A is formula(1) and B is formula(2)) selected from a reaction product of at least one polyfunctional compounds containing at least two diene groups and at least one polyfunctional compounds containing at least two compounds containing a dienophile group, and a reaction product of polyfunctional aromatic compounds containing at least one cyclopentadiene group and at least one acetylene group; and s solvent selected from the group consisting of N-methylpyrrolidone, γ-butyrolactone, mesitylene, cyclohexanone and their mixtures. The curable oligomer has a number average molecular weight of 3,500 or more and a mass average molecular weight of 5,400 or more.

Description

Polyphenylene oligomers, processes for coating such oligomers, and articles comprising the cured reaction product of such oligomers}

The present invention relates to a polyphenylene oligomer, a method of using the same, and a product manufactured using the same. The polyphenylene oligomers of the invention may be useful as dielectric resins in the manufacture of microelectronic devices.

The polymer dielectric may be used as an insulating layer located in metal interconnect layers in microelectronic devices such as integrated circuits or between metal interconnect lines between metal interconnect layers. The dielectric can also be used as an insulating layer in other microelectronic devices such as multichip modules and stacked circuit boards. The microelectronic device manufacturing industry is pursuing miniaturization of devices that can lower power consumption and speed up devices. The finer and more closely packed the conductors, the more stringent the condition of the dielectric placed between these conductors.

WO 98/11149 describes a wide range of polyphenylene oligomers and polymers that can be used as interlayer dielectrics in integrated circuits. However, Applicants have found that some compositions of oligomers in solvents are very sensitive to the effects of temperature and humidity during processing. In addition, WO 98/11149 discloses that when coated with this material, the oligomer must have a Mn (number average molecular weight) of less than 3000 and a Mw (weight average molecular weight) of less than 5200. Finally, this publication teaches that when the coating material is cured, it fills a rectangular trench with a depth of 1 μ and a width of 0.5 μ without leaving voids. Such polyphenylene compositions differ in composition for filling the gap and for inlay.

Applicants have found compositions containing larger molecular weight materials that can be covered and can fill gaps smaller than 0.5 microns. Applicants have also found compositions that can be used for gap filling or inlay in a single composition. In addition, Applicants have discovered compositions that wet out various surfaces better and are less sensitive to wider changes in humidity and temperature during processing. Finally, Applicants have found an improved composition that uses less raw material and wastes less during spin coating by allowing for less dispensing volume.

FIG. 1 shows a 0.18μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 2490. FIG.

Figure 2 shows a 0.18μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 4600.

Figure 3 shows a 0.40μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 4600.

Figure 4 shows a 0.18μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 6400.

FIG. 5 shows a 0.40μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 6400. FIG.

6 shows a 0.18μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 8875.

7 shows a 0.32μ gap filled with polyphenylene polymer having a number average molecular weight (Mn) of 8875.

In a first aspect, the present invention relates to at least one polyfunctional compound containing at least two diene groups, preferably cyclopentadienone groups and at least two dienophile groups, preferably acetylene groups. Reaction product (i) with at least one polyfunctional compound, wherein at least a minority of the polyfunctional compounds contain at least three reactive groups, at least one cyclopentadienone substituent group and at least one acetylene functional substituent A curable oligomer (a) comprising a reaction product selected from the reaction products (ii) of aromatic compounds comprising a group of N-methylpyrrolidinone (NMP), a mixture of NMP and cyclohexanone, of NMP and mesitylene Mixtures, gamma -butyrolactone, more preferably gamma -butyrolactone and mesitylene and gamma -butyrolactone and cyclohexanone A composition comprising in a solvent (b) selected from a mixture of

The number average molecular weight (Mn) of the oligomer is 3500 or more, preferably 4000 or more, preferably less than 6400, more preferably less than 6000, and the weight average molecular weight (Mw) is 5500 or more, preferably 8000 or more, preferably Is less than 15000, more preferably less than 12000. The polydispersity (Mw / Mn) of the oligomer is less than about 2.5, more preferably less than about 2.3. The composition can fill rectangular grooves with a depth of 1 μm and a width of less than 0.4 μm, preferably less than 0.35 μm, more preferably less than 0.3 μm, leaving no gaps upon curing. The composition is useful for damaging and exhibits excellent planarization properties. The composition preferably has 5 to 50% by weight, more preferably 5 to 35% by weight and most preferably 10 to 30% by weight, based on the weight of the solvent and the oligomer. The solvent mixture is preferably in the range of about 20:80 to 50:50 when solvent 1 is NMP or γ-butyrolactone and solvent 2 is cyclohexanone or mesitylene. Mixtures with γ-butyrolactone are preferred because of their resistance to high humidity, and especially mixtures of γ-butyrolactone with mesitylene. Trisolvent mixtures may also be used.

As used herein, a reactive group is defined as a diene or dienophilic group. Preferably, the diene is a cyclopentadienone group and the dienophilic group is an acetylene (preferably aromatic acetylene) group.

The high thermal stability, high glass transition temperature, low dielectric constant and gap filling ability and the ability to planarize the patterned surface make the compositions of the present invention suitable as polymer dielectrics in the manufacture of microelectronic devices. In particular, the combination of low dielectric constant, high thermal stability and high glass transition temperature allows the compositions of the present invention to be used as interlayer dielectrics in integrated circuits.

In a second aspect, the present invention provides a silicon wafer comprising at least a partial pattern of electrical internal connections and having a raised shape pattern, wherein a depth between the at least several raised shapes is at least about 1 micron and the width is about 0.4 gaps less than μ, preferably less than 0.35 μ), and the composition is coated onto the wafer, preferably with spin coating to form a thin film, followed by filling the gaps, followed by removal of the solvent, A method of making an integrated circuit product, including curing. Optionally, an adhesion promoter may be precoated on the substrate or added to the composition itself.

In a third aspect, the present invention provides a low dielectric constant material having a gate width of less than 0.20 μm, preferably less than 0.18 μ, and having an electrical internal connection structure comprising a pattern of metal wires, which at least partially separates the metal wires. Cured reaction product of at least one multifunctional compound containing a diene group, preferably a cyclopentadienone group, with at least one polyfunctional compound containing two or more dienophilic groups, preferably an acetylene group, wherein A minority of the polyfunctional compounds contains at least three reactive groups). An integrated circuit product comprising an active substrate on which a transistor is mounted.

In a fourth aspect, the present invention provides a substrate, applies the composition of the extinguishing capacity to the substrate, and then spins the substrate at about 2500 to about 4000 revolutions per minute to form a coating on the substrate, A method of making a coated article, including drying, where the coating has a volume of dissipation capacity of at least 0.01%.

Preferably, the oligomers and corresponding starting monomers of the invention are as follows:

I. Oligomers of Formula 1.

[A] _w [B] _z [EG] _v

In Formula 1 above,

A is a chemical formula Wherein R ¹ and R ² are independently H or an aromatic moiety that is unsubstituted or substituted with an inert group, and Ar ¹ and Ar ² are independently an aromatic moiety that is unsubstituted or an aromatic moiety substituted with an inactive group,

B is a chemical formula Wherein R ¹ and R ² are independently H or an aromatic moiety unsubstituted or substituted with an inert group, Ar ¹ and Ar ³ are independently an unsubstituted aromatic moiety or an aromatic moiety substituted with an inert group, and M is Is a bond, p is the number of unreacted acetylene groups in a given mer unit, r is one less than the number of acetylene groups reacted in a given mer unit),

EG is

Wherein R ¹ and R ² are independently H, an unsubstituted or substituted aromatic moiety, and Ar ¹ , Ar ² and Ar ³ are independently unsubstituted aromatic moieties or substituted by inert groups Y is an integer of at least 3, and p + r = y-1)

z is an integer of 0 or more,

w is an integer of 0 or more,

At least one z or w is 1,

v is an integer of 2 or more,

The upper limit of z + w + v is selected such that the range of average molecular weights is specified herein, preferably z + w + v is less than about 20 for the oligomer.

Clearly, when the oligomer cures to form a polymer in the final product, z + w + v is much larger, each potentially reaching a value of 1000 or more.

Such oligomers can be prepared by reacting biscyclopentadienone, aromatic acetylene containing three or more acetylene residues and, optionally, multifunctional compounds containing two or more aromatic acetylene residues. This reaction is a chemical formula Bicyclopentadienone (a), wherein R ¹ and Ar ¹ are the same as defined above, Of polyfunctional acetylene (b), wherein R ² , Ar ² and y are as defined above, and, optionally, Can be represented by the reaction of diacetylene (c), wherein R ² and Ar ² are the same as defined above.

Definitions of aromatic moieties include phenyl, polyaromatic and fused aromatic moieties. "Substituted with inert groups" means that the substituent groups are essentially inert to cyclopentadienone and acetylene polymerization and do not readily react with environmental species such as water under conditions using polymers cured in microelectronic devices. . The substituent group is, for example, F, includes a cycloalkyl of _{Cl, Br, -CF 3, -OCH} 3, -OCF 3, -O-Ph, alkyl and a carbon number of 1 to 8 carbon atoms from 3 to 8. For example, residues that may be unsubstituted or aromatic residues substituted with inert groups are

[Where Z is -O-, -S-, alkylene, -CF _2- , -CH _2- , -O-CF _2- , perfluoroalkyl, perfluoroalkoxy,

Wherein R ³ are each independently —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ or Ph, and Ph is phenyl].

II. Polyphenylene oligomers of Formula 2:

In Formula 2 above,

Ar ⁴ is an aromatic moiety substituted with an aromatic moiety or an inert group,

R ¹ and R ² are as defined above,

x is chosen to be the desired molecular weight.

Such compounds have the formula It can be prepared by reacting a cyclopentadienone functional group and an acetylene functional group of the polyfunctional compound (wherein R ¹ , R ² and Ar ⁴ are as defined above).

III. Chemical formula Cyclopentadienone functional groups of a multifunctional compound of wherein R ¹ and R ² are independently H, an unsubstituted or substituted aromatic moiety, and Ar ⁴ is an aromatic moiety substituted with an aromatic moiety or an inactive group. A polyphenylene oligomer of formula (3) which may be prepared by reacting with an acetylene functional group:

In Formula 3 above,

P represents the growing branched oligomer / polymer chain and is represented by the formula Has a repeating structure of,

G is a terminal group that fills the valence where oligomer / polymer growth does not occur Has the structure of

R ¹ and Ar ⁴ are as defined above,

j and k are integers greater than or equal to 1

J + k is 3 or more,

n and m are integers greater than or equal to zero,

Provided that n + m is 1 or more.

Multifunctional compounds containing two or more aromatic cyclopentadienone moieties can be prepared by condensing benzyl into benzyl ketones using conventional methods. Exemplary methods are described in Kumar et al., Macromolecules, 1995, 28, 124-130; Oliaruso et al., J. Org. Chem., 1965, 30, 3354; Ogliaruso et al., J. Org. Chem., 1963, 28, 2725 and US Pat. No. 4,400,540.

Multifunctional compounds containing two or more aromatic acetylene moieties can be prepared by conventional methods. The halogen can be substituted with a substituted acetylene compound by halogenating the aromatic compound and then reacting with a suitable substituted acetylene in the presence of an aryl ethynylation catalyst.

Once the polyfunctional compound monomers are prepared, it is desirable to purify them. In particular, metals and ionic species are removed when prepared for use as an organic polymer dielectric. For example, polyfunctional compounds containing aromatic acetylene groups are washed with water and contacted with aliphatic hydrocarbon solvents, dissolved in aromatic solvents and filtered over purified silica gel. This treatment can remove residual ethynylation catalyst. Further recrystallization can also help remove unwanted impurities.

Although not wishing to be bound by theory, the Diels Alder reaction of cyclopentadienone and acetylene forms a polyphenylene oligomer and polymer when the mixture of cyclopentadienone and acetylene in the solution is heated. It is believed to be. Such oligomers may contain cyclopentadienone and / or acetylene end groups and / or pendant groups. When further heating this solution or the product coated with this solution, further chain extension may occur through Diels Alder reaction of the remaining cyclopentadienone end group with the remaining acetylene group, resulting in an increase in molecular weight. Depending on the temperature used, reactions between acetylene groups can also occur.

Oligomers and cured polymers exhibit structures with cyclopentadienone and / or acetylene end groups and / or pendant groups. In general, the end groups depend on the relative concentration of cyclopentadienone relative to the Diels-Alder-reactive acetylene functional groups used in the reaction, with stoichiometric excess of cyclopentadienone functional groups providing more cyclopentadienone end groups and stoichiometric The theoretical excess of Diels-Alder-reactive acetylene functionality provides a greater proportion of acetylene end groups.

Without wishing to be bound by theory, the preparation of polyphenylene polymers can generally be represented as follows:

In Scheme 1 above,

R ¹ , R ² , Ar ¹ , Ar ² and x are as defined above.

In addition, although not specifically shown in the formula, several carbonyl bridged species may be present in the oligomers prepared, depending on the specific monomers used and the reaction conditions. Upon further heating, the carbonyl bridged species will be converted almost completely to an aromatic ring system. When one or more acetylene containing monomers are used, the oligomers and polymers formed are not constant, but the formula shown may suggest that blocks are formed. Cyclopentadienone can react with Diels Alder in the acetylene functional period to form an attachment in the para or meta position to the phenylated ring.

The monomers can be in b-stage by known methods. Preferably, however, the monomers become b-states in γ-butyrolactone or NMP to form oligomers, followed by addition of cyclohexanone or mesitylene.

The composition of the b-state oligomer in the solvent system is coated on the substrate and cured. One preferred use of the cured material is as an interlayer dielectric. Subtractive processes or inlays can be used to make devices having cured polymers as interlayer dielectrics. The composition of the present invention has good gap filling properties. The compositions of the present invention also have good planarization properties.

After coating the composition, the solvent is removed by heating, preferably the oligomer is cured. Temperatures of at least 300 ° C., preferably at least 375 ° C., most preferably at least 400 ° C., may be used to cure. The sample can be cured by various means, including a hot plate or a furnace.

Example 1

Preparation of Cyclopentadienone Compound and Acetylene Compound

1.1,3,5-tris (phenylethynyl) benzene

Triethylamine (375 g), triphenyl phosphine (4.7865 g), palladium acetate (1.0205 g) and N, N-dimethyl formamide (2000 ml) were prepared with a thermocouple, top mechanical stirrer, cooler, addition funnel, and temperature controller. Fill a 5-liter three-neck round bottom flask equipped with a heating mantle. The mixture is stirred for 5 minutes to dissolve the catalyst. Then, diethylhydroxylamine (5 g), 1,3,5-tribromobenzene (190 g) and phenylacetylene (67.67 g) are added. The reactor is purged with nitrogen for 15 minutes and then heated to 70 ° C. while maintaining a nitrogen atmosphere. After heating at 70 ° C. for 30 minutes, phenylacetylene (135.33 g) is slowly added dropwise over about 1 hour and the temperature is raised to 80 ° C. Continue heating for an additional 9 hours. The reaction is then cooled to room temperature and water (1 L) is added to precipitate the crude product. The product is filtered and washed three times with 500 ml of water and then once with 500 ml of cyclohexane. The crystals were dried under reduced pressure at 75 ° C. overnight to yield 226.40 g (99.1% yield) of 97.25 area% purity by gas chromatography. The crystals are dissolved in toluene (1800 ml), refiltered with silica gel and the solvent is removed by rotary evaporation to give 214.2 g (94.2% yield) of 99.19 area% purity by gas chromatography. The residue is then recrystallized from a mixture of toluene (375 ml) and 2-propanol (696 ml). The white crystals were filtered off, washed with a mixture of toluene (100 ml) and 2-propanol (400 ml), and dried under reduced pressure at 75 ° C. overnight to obtain 1,3,5-tris (phenyl) having a purity of 99.83 area% by gas chromatography. Tinyl) benzene (190.0 g, 83.91% yield). Further recrystallization from toluene / isopropanol yields materials of acceptable organic and ionic material purity.

2. 4,4'-bis (phenylethynyl) diphenyl ether

In a 1 L three-necked round bottom flask with thermocouple, equipped with a heating mantle with a top mechanical stirrer, cooler and temperature controller, triethylamine (111.5 g), triphenyl phosphine (1.158 g), palladium acetate (0.2487 g), di Charge ethylhydroxylamine (1.24 g), 4,4'-dibromodiphenyl ether (68.6 g), phenylacetylene (67.74 g), N, N-dimethyl formamide (136 ml) and 72 ml water. The reactor is purged with nitrogen for 15 minutes and then heated to 90 ° C. for 19 hours while maintaining a nitrogen atmosphere. The reaction is then cooled to room temperature and water (80 ml) is added. The crude product was filtered off and the solid was washed once with 120 ml of toluene and four times with 160 ml of water, and 4,4'-bis (phenylethynyl) having a purity of 99.64 area% by gas chromatography when dried overnight under vacuum. 66.37 g (85.6% yield) of fine white needles of diphenyl ether are obtained.

3. 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone)

(a) Preparation of 4,4'-diphenylacetyldiphenyl ether

To a slurry of aluminum chloride (97.9 g, 0.734 mol) in methylene dichloride (200 ml) was added a solution of diphenyl ether (50.0 g, 0.294 mol) and phenylacetyl chloride (102 g, 0.661 mol) in methylene chloride (50 ml) at 0 ° C. Add dropwise for 30 minutes. When the addition is complete, the reaction mixture is warmed to ambient temperature and stirred overnight. The reaction mixture is carefully poured into 1.5 kg of ice / water with stirring. Methylene chloride (1500 ml) is added to dissolve the solids and separate the layers. The organic layer is filtered through celite and concentrated to dryness. Recrystallization from toluene yields 110 g (92%) of the title compound as a light tan prism.

(b) Preparation of 4,4'-bis (phenylglyoxaloyl) diphenyl ether

Aqueous HBr (97 ml of 48 wt% solution) was added to a slurry of 4,4'-diphenylacetyldiphenyl ether (50.0 g, 0.123 mol) in DMSO (400 ml) and the resulting mixture was heated to 100 ° C. for 2 hours. Then cooled to ambient temperature. The reaction mixture is partitioned between toluene (500 ml) and water (750 ml). The organic layer is washed with water (3 × 250 ml), then brine and concentrated to give a viscous light yellow oil which solidifies upon standing at ambient temperature. Recrystallization from ethanol affords 35.9 g (67%) of the title compound as a light yellow cube.

(c) Preparation of 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone)

195.4 g (4,498 mol, 1.0eq), 193.9g (0.9220mol, 2.05eq) of diphenylacetone and 2.5L of deoxygenated ethanol are added. The mixture is heated to reflux, whereby a homogeneous solution is sparged with nitrogen for 30 minutes. To the addition funnel add 25.2 g of KOH (0.4498 mol, 1.0 eq), 200 ml of ethanol and 25 ml of water. The temperature is lowered to 74 ° C. and the KOH solution is added rapidly over 5 minutes. Exothermic reactions occur rapidly and continue to reflux until 3/4 of the solution is added, after which the temperature begins to drop. As soon as the base is added, dark purple is observed and a solid is observed before the addition is complete. After the addition is complete, the heterogeneous solution is heated with vigorous reflux for 15 minutes to form a large amount of solid product. The mixture is cooled to 25 ° C. and 29.7 g (0.4948 mol, 1.1 eq) of glacial acetic acid are added and stirred for 30 minutes. The crude product was isolated by filtration, washed with 1 liter of water, 3 liters of EtOH and 2 liters of MeOH in a filtration funnel and dried at 60-90 ° C. for 12 hours under vacuum to give 323 g of crude DPO-CPD (94% purity 94%) by LC. %) Is obtained. The crude material is dissolved in HPLC grade methylene chloride (10% by weight) and transferred to a 5L Morton flask equipped with a lower flush valve and mechanical stirrer and washed vigorously 2-7 times with the same volume of low ion water for 10-90 minutes. The CH ₂ Cl ₂ solution is flowed through a 5 cm column containing 75 g of silica gel in CH ₂ Cl ₂ . The column is washed with additional 1 L CH ₂ Cl ₂ , where the filtrate is almost transparent. The solution is evaporated to dryness, redissolved in THF and evaporated again to remove most of the remaining methylene chloride. The powder is transferred to a 5 L flask equipped with an addition funnel and Friedrich's reflux cooler and dissolved (0.07 to 0.12 g / ml) with deoxygenated HPLC THF under reflux. Then additional 1 L THF is added and a nitrogen sparging tube is inserted into the solution. The solution is sparged with nitrogen for 3 hours and the remaining methylene chloride is distilled off and cooled at 45-50 ° C. while removing THF. The distillation head is attached and 700 ml to 1 L of THF is removed. The solution is slowly cooled to room temperature over several hours and then cooled to less than 10 ° C. with an ice bath, during which crystallization occurs. Crystals are separated using a 5 mm PTFE filter in a 4 L Millipore clamp-frit suction filtration flask. The crystals are then washed with lL MeOH and dried under vacuum at 80-90 ° C. overnight to give DPO-CPD with a 99% LC purity and mp 270 ° C. in 70-85% yield.

Comparative Example 2

High purity 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (971.0 g, 1.24 mol), high purity 1,3,5-tris (Phenylethynyl) benzene (469.1 g, 1.24 mol) and electronic grade N-methylpyrrolidone (2163.1 g) are added to a 5 L flask. The flask is attached to a nitrogen / vacuum inlet. The magnetically stirred solution is degassed by applying vacuum and backfilled with nitrogen five times. Nitrogen gas is allowed to flow into the headspace of the flask and discharged through a mineral oil bubbler. The solution is heated at 200 ° C. for 10 hours. The molecular weight (Mn) of the oligomers measured by gas permeation chromatography is 2490 based on polystyrene standards. The solution is cooled to room temperature and then diluted to 1199.8 g of electronic grade cyclohexanone before being bottled. Before coating the wafer, a portion of the solution is diluted to viscosity 11.1 cSt with additional electronic grade cyclohexanone. The solution is filtered through a 0.1μ Teflon ^™ polymer filter to remove residual particles. Ionic impurities measured by ICP-MS are less than 200 ppb of sodium, potassium, copper, nickel and iron, respectively.

3 ml of the silane adhesion promoter AP8000, commercially available from The Dow Chemical Company, is first extruded onto the surface of a 200 mm wafer configured to have a gap in the range of 0.18 to 0.4 μ. The accelerator is slowly withdrawn and dispersed over the entire surface, left for 2 seconds and finally spinning dried at 3000 rpm for 10 seconds. 2 ml of polyphenylene oligomer solution is coated onto the surface of a 200 mm wafer coated with an adhesion promoter by Millipore Gen-2, a high precision pump / filtration system, spinning at 60 rpm. The temperature and relative humidity of the coater are 27 ° C. and 25% RH. Wafer rotation is accelerated to 2000 rpm immediately after coating of the oligomer solution and maintained at this spin rate for 30 seconds. A continuous stream of mesitylene is coated on the backside of the wafer for 5 seconds while coating the oligomer solution. The 2 mm to 5 mm end beads of the coating are removed with a continuous stream of mesitylene while spinning at 2000 rpm by coating the wafer from the back or directly from near the top end. After removal of the terminal beads, the oligomer is further polymerized in a hotplate at 320 ° C. for 90 seconds under a nitrogen blanket. The film is then crosslinked on a 450 ° C. hotplate for 2 minutes under nitrogen or in a nitrogen purged oven at 400 ° C. for 30 minutes. After samples were prepared using a focused ion beam (FIB), SEM analysis of the coated wafer indicated that 0.18 μ of gap was completely filled by the polymer (FIG. 1). Polymeric coatings also exhibit good planarization properties.

Example 3

Of oligomer solution from 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) and 1,3,5-tris (phenylethynyl) benzene Produce

High purity 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) 970.2 g (1.24 mol), 1,3,5-tris (phenylethynyl 469.0 g (1.24 mol) benzene and 2160.5 g of electronic grade γ-butyrolactone are added to a 5 L flask.

The flask is attached to a nitrogen / vacuum inlet. The magnetically stirred solution is degassed by applying vacuum and backfilled with nitrogen five times. Nitrogen gas is allowed to flow into the flask's headspace and released into the mineral oil bubbler. The solution is heated to an internal temperature of 200 ° C. After heating for 14 hours, the solution is cooled to room temperature, diluted with 1199.3 g of mesitylene and transferred to the bottle. Analysis of the final solution by gel permeation chromatography shows that M _n is 4600 based on polystyrene standards. A portion of the solution is diluted to a viscosity of 15.6 cSt with additional electronic grade mesitylene before coating the wafer. The solution is filtered through a 0.1 μ filter to remove residual particles. Ionic impurities measured by ICP-MS are less than 200 ppb of sodium, potassium, copper, nickel and iron, respectively.

The Dow Chemical Company commercially available AP4000, a silane-based adhesion promoter, is first coated on the surface of a 200 mm wafer configured to have a gap of 0.18 to 0.4 μm in width as described in the following table.

Dissipation capacity 3 ml Dissipation rate 750 rpm Burnout time 5 sec Drying acceleration 10000 rpm / s Drying rate 3000 rpm Drying time 30 seconds

The wafer is coated with an adhesion promoter and then back treated at 180 ° C. for 60 seconds.

2 ml of the polyphenylene solution prepared above is coated at 60 rpm on a wafer surface coated with an adhesion promoter by Millipore Gen-2, a high precision pump / filtration system. Immediately after the oligomer solution is drained, the wafer is accelerated to 3000 rpm with an acceleration of 10000 rpm / second and dried for 30 seconds. A continuous stream of mesitylene is coated on the backside of the wafer for 5 seconds while the oligomer solution is withdrawn. The 2 mm to 5 mm end beads of the coating are removed with a continuous stream of mesitylene while spinning at 2000 rpm by directly covering the wafer from near the upper end. After removal of the terminal beads, the oligomer is further polymerized in a 320 ° C. hotplate for 90 seconds under a nitrogen blanket. The film is then crosslinked in a nitrogen purged oven at 400 ° C. for 30 minutes. After making samples using focused ion beams (FIBs), SEM analysis of the coated wafer showed that the gap of 0.18μ and the gap of 0.4μ were completely filled by the polymer (FIGS. 2 and 3). Polymeric coatings also exhibit good planarization properties.

Comparative Example 4

Polyphenylene oligomer solution is prepared as described in Example 3, except that the solution is heated for a total of 22 hours. The molecular weight (M _n ) of this solution is 6400 based on polystyrene standards. Dilute the solution to viscosity 18.7 cSt using mesitylene.

AP4000, a silane-based adhesion promoter sold by The Dow Chemical Company, is coated on the surface of a wafer configured to have a gap in the range of 0.18 to 0.4 mu as described in Example 3. The oligomer solution is coated and cured on the wafer as described in Example 3.

Samples are prepared by curing the wafer using FIB and then analyzing the gap using SEM. Both 0.18 and 0.40μ gaps are incompletely filled (FIGS. 4 and 5). Planarization is also not as good as in Comparative Examples 2 and 3.

Comparative Example 5

A polyphenylene oligomer solution is prepared as described in Example 3 except that the solution is heated for a total of 48 hours and then diluted with cyclohexanone instead of mesitylene. The molecular weight (M _n ) of this solution is 8875 based on polystyrene standards. Additional cyclohexanone is used to dilute the solution to viscosity 18.7 cSt.

AP4000, a silane-based adhesion promoter sold by The Dow Chemical Company, is coated on the surface of a wafer configured to have a gap in the range of 0.18 to 0.4 mu as described in Example 3. 2 ml of oligomer solution is coated and cured as described in Example 3.

Samples are prepared by curing the wafer using FIB and then analyzing the gap using SEM. Both 0.18 and 0.32μ gaps are incompletely filled (FIGS. 6 and 7). Planarization is also not as good as in Comparative Examples 2 and 3.

Example 6

Polyphenylene oligomer solution is prepared as in Example 3. The solution is diluted with sufficient mesitylene to produce a film of 7000 kPa while spin coating at 2500-4000 rpm. The solution has 24.7% γ-butyrolactone, 56.8% mesitylene and 18.5% solids and has a viscosity of 8.7 cSt. The 200 mm silicon wafer is coated with an adhesion promoter and oligomer solution as described in Example 3, except that 1.25 ml of the diluted oligomer solution is extruded onto the wafer. Full wafer coverage with a 1.25 ml extruding capacity is observed. After coating and drying, at least 0.01% by volume of solution remains on the wafer.

Comparative Example 7

A polyphenylene oligomer solution is prepared as described in Comparative Example 5 and diluted with sufficient cyclohexanone to produce a film of 7000 kPa while spin coating at 2500-4000 rpm. The solution has 69.7% cyclohexanone, 17.3% γ-butyrolactone and 13.3% solids and has a viscosity of 17.7 cSt. The 200 mm silicon wafer is coated with an adhesion promoter and oligomer solution as described in Comparative Example 5 except that 1.25 ml of the solution is flushed onto the wafer. Incomplete wafer coating with 1.25 ml dissipation capacity is observed. The dissipation capacity is increased until complete coating is observed. At least 1.8 ml of dissipation capacity is required for complete wafer coating. After coating and drying, only 0.007% by volume of solution remains on the wafer.

The oligomer composition of the present invention can be used for filling gaps and inlays in a single composition, and can be completely coated with a small dissipation capacity, so that less raw material is used and less waste during spin coating.

Claims (9)

Reaction product (i) of at least one multifunctional compound containing at least two diene groups with at least one polyfunctional compound containing at least two dienophile groups, wherein at least one of the multifunctional compounds The minority contains at least three reactive groups) and a curable oligomer (a) selected from the group comprising reaction products (ii) of polyfunctional aromatic compounds having at least one cyclopentadienone group and at least one acetylene group, wherein The number average molecular weight of the oligomer is 3500 or more and the weight average molecular weight is 5400 or more) in a solvent (b) selected from N-methylpyrrolidinone, γ-butyrolactone, mesitylene, cyclohexanone and mixtures thereof. Composition. The process of claim 1 wherein the curable oligomer is of formula Bicyclopentadienone (a), wherein R ¹ is H or an aromatic moiety that is unsubstituted or substituted with an inert group, and Ar ¹ is an unsubstituted aromatic moiety or an aromatic moiety substituted with an inactive group Polyfunctional acetylene (b) wherein R ² is H or an aromatic moiety that is unsubstituted or substituted by an inert group, Ar ³ is an unsubstituted aromatic moiety or an aromatic moiety that is substituted by an inactive group, and y is an integer of 3 or more And, optionally, a chemical formula A reaction product of diacetylene (c), wherein R ² is H or an unsubstituted or substituted aromatic moiety and Ar ² is an unsubstituted aromatic moiety or an aromatic moiety substituted by an inert group. The composition of claim 1, wherein a rectangular groove having a depth of 1 μ and a width of less than 0.4 μ is filled so that there is no gap after the oligomer has cured. The composition of claim 1, wherein the solvent comprises a mixture of γ-butyrolactone with one or more mesitylene or cyclohexanone. The composition of claim 1 wherein the solvent is a mixture of γ-butyrolactone and mesitylene. The composition according to any one of claims 1 to 5, wherein the number average molecular weight is less than 6400. Providing a silicon wafer comprising at least a partial pattern of electrical internal connections and having a raised shaped pattern, wherein there are gaps of at least 1 micron in depth and less than about 0.4 microns in width between the at least several raised shapes; A method of making an integrated circuit product comprising coating a composition according to claim 3 on a wafer to form a thin film, then filling the gaps, then removing the solvent, and then curing the composition. Providing a substrate, providing a composition according to claim 1 of a dispensing volume, and then applying a composition of dissipating capacity to the substrate, and then rotating the substrate at about 2500 to about 4000 revolutions per minute Spinning to distribute the composition throughout the substrate to form a coating, and then drying the coating, where the coating has a volume of dissipation capacity of at least 0.01%. Low dielectric constant materials that have an electrical interconnect structure comprising a pattern of metal wires with a gate width of less than 0.20 μ and at least partially separate the metal wires, including at least one polyfunctional compound containing at least two diene groups and at least two dienophiles Characterized in that the reaction product with at least one polyfunctional compound containing a functional group, where a minority of the polyfunctional compounds contains at least three reactive groups, is a cured product of an oligomer. And an active substrate on which the transistor is mounted.