CN114989762B

CN114989762B - Conductive adhesive for single-component semiconductor and preparation method thereof

Info

Publication number: CN114989762B
Application number: CN202210746384.6A
Authority: CN
Inventors: 陈伊凡; 黄成生
Original assignee: Nantong Deju Semiconductor Materials Co ltd
Current assignee: Nantong Deju Semiconductor Materials Co ltd
Priority date: 2022-06-29
Filing date: 2022-06-29
Publication date: 2023-06-23
Anticipated expiration: 2042-06-29
Also published as: CN114989762A

Abstract

The invention relates to a single-component conductive adhesive for a semiconductor and a preparation method thereof, wherein the conductive adhesive comprises the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 4-8 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 5-10 parts of diluent; the acid anhydride curing agent comprises a polymer containing acid anhydride. The single-component semiconductor conductive adhesive prepared by the invention has excellent comprehensive performance, good conductivity, lower storage modulus, excellent high temperature resistance and damp-heat resistance. As can be seen from comparison of examples and comparative examples, the conductive adhesive of the invention can achieve satisfactory degree in all performance indexes simultaneously by specific selection of each component, in particular to multi-functional fused polycyclic epoxy resin in epoxy resin, epoxy POSS and compounding of curing agent with end group as acid anhydride and side chain as acid anhydride in curing agent.

Description

Conductive adhesive for single-component semiconductor and preparation method thereof

Technical Field

The invention relates to the technical field of semiconductor packaging and bonding, in particular to a single-component conductive adhesive for a semiconductor.

Background

With the development of electronic technology, the development trend of circuit boards is the requirements of smaller size (such as thinner and smaller volume), lighter weight (high integration level), multifunction and intellectualization. Also, higher demands are being placed on the packaging technology of electronic components. The conductive adhesive is used as a novel solder for replacing the traditional solder; the environment-friendly material has the advantages of simple operation process and low bonding temperature. As a bonding material for chips and substrates, it is necessary to have high bonding strength, electric conduction and heat conduction, and whether or not it is reliable directly affects the use condition, stability and lifetime of electronic components.

The current conductive adhesive for electronic components mainly comprises epoxy resin, conductive filler, curing agent, curing accelerator and all auxiliary materials. The epoxy resin used contains polar groups such as ester groups and hydroxyl groups, and thus tends to have a certain water absorption property, and the main resin used as the encapsulating material is not resistant to heat and humidity. Under the conditions of high temperature and high humidity, chemical corrosion and the like can occur, so that the contact resistance between the conductive adhesive and the substrate is increased, and the reliability of the electronic component is reduced. The conductive adhesive is mainly applied to packaging and bonding of electronic components such as a liquid crystal display, an LED, an IC chip, a printed circuit board and the like, and often needs a high-temperature use environment. Particularly, the existing technology of electronic components basically adopts a reflow soldering technology, the temperature is up to 260 ℃, the high temperature resistance of the existing conductive adhesive is poor, the Tg is lower, the bonding performance is obviously reduced above 200 ℃, and the processing technology requirements of the existing electronic components cannot be met.

The damage mode of the conductive adhesive is also an evaluation index of the conductive adhesive. The conductive adhesive is destroyed mainly by 1) cohesive failure: the damage occurs in the layer of the conductive adhesive, and the cohesive damaged substrate surface has residual adhesive from the appearance, and the damage mode can obtain the maximum bonding strength during the adhesive; 2) Interface disruption: namely, the damage occurs at the interface between the adhesive and the adherend;

3) Mixing and breaking: i.e., cohesive failure and interfacial failure are present at the same time. The conductive paste used as the encapsulating material for electronic components is expected to be cohesive failure when broken. Cohesive failure demonstrates the optimal bonding between the glue and the substrate, and is easier to pass through a series of tests of reliability such as high temperature, high humidity, aging, etc.

In addition, the improvement of the adhesive strength, particularly at high temperature, often contradicts with the storage modulus, and the improvement of the adhesive strength of the conductive adhesive also often increases the storage modulus, and further increases the warp deformation phenomenon caused by the environmental temperature change. Thus, how to obtain a combination of high bond strength and low storage modulus is a problem that has been difficult to solve in the art.

CN109504327a discloses a high Tg high reliability epoxy potting conductive adhesive, which uses bismaleimide triazine modified epoxy resin to greatly increase Tg of the conductive adhesive, but has a higher storage modulus, so that warp deformation generated when the ambient temperature changes cannot be overcome. CN112358841a discloses a flexible conductive adhesive, wherein the epoxy acrylate with an organosilicon block is adopted, so that the storage modulus is reduced, the flexibility of the conductive adhesive is improved, but the Tg is lower, the high temperature resistance is poor, and the requirement of the semiconductor conductive adhesive cannot be met.

Cage Polysilsesquioxane (POSS), an organosilicon compound, has a cage-like structure, with groups on the Si atoms at its top corners being able to attach different functional groups by a rich chemical strategy. Its particular nature and abundant chemical modification are involved in applications in a number of fields. Epoxy POSS is a POSS derivative in which a single or multiple epoxy groups are introduced into the compound framework of a cage polysilsesquioxane. The application of epoxy POSS in the field of adhesives has been disclosed in many prior arts, such as epoxy POSS with different epoxy functionalities is adopted in CN112708325A, and the curing agent is anhydride-terminated polyether, which achieves the hardness and toughness of the epoxy resin coating by combining the rigid group of POSS with the polyether soft segment in the anhydride curing agent. However, the curing speed of the patent is slower, and the moisture and heat resistance needs to be improved by singly adopting epoxy POSS.

Disclosure of Invention

In order to solve the defects that the conductive adhesive in the prior art has insufficient high-temperature adhesion (the failure mode is mainly interface failure), insufficient wet heat aging resistance and difficult balance of adhesive strength and storage modulus, the invention provides the conductive adhesive for the semiconductor, which has the advantages of cohesive failure in the failure mode, high adhesive strength under the conditions of high temperature and wet heat, low storage modulus and high reliability.

The invention solves the technical problems by the following technical proposal:

the single-component conductive adhesive for the semiconductor comprises the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 4-8 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 5-10 parts of diluent; the acid anhydride curing agent comprises a polymer containing acid anhydride.

The conductive adhesive for the single-component semiconductor has high reliability, and various performance indexes can meet the requirements under the high-temperature (260 ℃) and damp-heat (85 ℃,85 RH%) environments.

Further, the epoxy POSS has a chemical structure as shown in the following formula (I):

each R is independently 2, 3-glycidoxypropyl, 3, 4-epoxycyclohexylethyl.

Further, the epoxy resin includes a novolac epoxy resin, a bisphenol epoxy resin and a polyfunctional condensed polycyclic epoxy resin; the epoxy value of the phenolic epoxy resin and the bisphenol epoxy resin is 0.4-0.6, and the functionality of the polyfunctional condensed polycyclic epoxy resin is 3-6.

Further, in the epoxy resin, the mass ratio of the phenolic epoxy resin, the bisphenol epoxy resin and the polyfunctional condensed polycyclic epoxy resin is 15-20:10-15:3-6.

Still further, the polyfunctional fused polycyclic epoxy has a functionality of 4, specifically selected from the group consisting of:

at least one of (a) wherein A is +.>

* Represents a site linked to a phenyl group, R is independently selected from the group consisting of H, C C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl.

The condensed polycyclic epoxy resin with the functionality of 4 is obtained by a preparation method comprising the following steps: dissolving a precursor compound containing four phenolic hydroxyl groups in an organic solvent, adding a catalyst, heating to 80-90 ℃ under nitrogen atmosphere, slowly adding excessive epichlorohydrin, reacting for 4-8h, cooling to 60-70 ℃, adding an aqueous solution of NaOH, reacting for 3-5h, distilling under reduced pressure to remove the solvent and the excessive epichlorohydrin, and drying to obtain the epoxy chloropropane.

The precursor compound containing four phenolic hydroxyl groups is a compound in which the group A is replaced by a hydroxyl group in the polyfunctional condensed polycyclic epoxy resin, namely

Further, the organic solvent is at least one selected from isopropanol, dichloromethane and ethyl acetate, and the catalyst is tetrabutylammonium bromide. The excessive epichlorohydrin is 15-20 times of the mol amount of the precursor compound containing four phenolic hydroxyl groups; the mass fraction of the NaOH aqueous solution is 30-40wt%, and NaOH is added in a plurality of batches, for example, 2-5 batches, wherein the difference of each batch is not more than 20%, and the addition of NaOH is preferably gradually decreased; the amount of NaOH added is not particularly limited, and the epoxidation dechlorination reaction can be carried out, and the amount of NaOH added is generally 15-25wt% of the mass of epichlorohydrin.

The acid anhydride curing agent comprises a small molecule acid anhydride curing agent and a high molecule acid anhydride curing agent, and the small molecule acid anhydride curing agent is well known in the field, such as at least one of maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, dodecenyl succinic anhydride and 4-methylhexahydrophthalic anhydride; the anhydride of the macromolecular anhydride curing agent is positioned at the end group and/or the side chain of the macromolecule.

Further, the polymer acid anhydride curing agent with acid anhydride at the end group is polysiloxane with acid anhydride at the end group, and the structure is at least one of the following formulas (B1), (B2) and (B3):

wherein R is ₁ Independently selected from H and methyl.

The macromolecular anhydride curing agent with the anhydride at the end group shown in (B1), (B2) and (B3) is prepared by a preparation method comprising the following steps: the polysiloxane and unsaturated anhydride are subjected to Si-H addition reaction to obtain the modified polysiloxane.

Further, in the above preparation method, the unsaturated acid anhydride is selected from maleic anhydride, norbornenedianhydride or itaconic anhydride, such as a platinum-based catalyst. The reaction conditions for Si-H addition are well known in the art, i.e., in the presence of a platinum-based catalyst, at 70-90℃for 20-30 hours under an inert atmosphere.

Further, the macromolecular anhydride curing agent with anhydride at the side chain is maleic anhydride modified liquid polybutadiene.

Preferably, the curing agent is a small molecule anhydride curing agent, polysiloxane with an anhydride end group, and maleic anhydride modified liquid polybutadiene, and the mass ratio is 5-10:10-15: 4-7.

The inventors have unexpectedly found that the above-mentioned epoxy resin, particularly the condensed polycyclic epoxy resin having a functionality of 4, is compounded with the above-mentioned compounded curing agent, namely, a curing agent containing a conventional small-molecule acid anhydride and also a high-molecule curing agent containing an acid anhydride as a terminal group/side chain, in combination. The interaction of multiple components can obviously improve the comprehensive properties of the conductive adhesive, including mechanical properties, heat resistance and moist heat resistance. The possible reasons are presumed that the polymer curing agent with the end group as acid anhydride and the polymer curing agent with the side chain as acid anhydride have certain complementary effects, and the toughness and the strength of the conductive adhesive are enhanced together by matching with the polyfunctional epoxy resin, so that the phenomenon that various indexes are difficult to improve synchronously can not occur, and particularly, the adhesive strength and the low storage modulus are obtained simultaneously.

The diluent is a reactive diluent with epoxy groups which is conventional in the art, and is specifically at least one selected from tert-butylphenyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and o-tolylglycidyl ether.

The conductive filler is not particularly limited, and a conductive filler is generally used in the art. Such as silver powder, silver-plated copper powder, silver-plated nickel powder, silver-plated plastic powder, etc.; the conductive filler is spherical powder, flaky powder or dendritic powder, and has a particle size of 0.1-10 μm.

The curing accelerator is imidazole curing accelerator, and is specifically selected from at least one of 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.

Preferably, the single-component semiconductor conductive adhesive further comprises some auxiliary materials, and the types, functions and the dosage of the auxiliary materials are well known in the art. For example, the conductive adhesive for the single-component semiconductor further comprises 0.05-0.2 part of anti-settling agent and 0.1-0.5 part of coupling agent.

The anti-settling agent is selected from fumed silica, and the coupling agent is selected from gamma-glycidoxypropyl trimethoxysilane.

The second object of the present invention is to provide a method for preparing the highly reliable conductive paste for single-component semiconductors, comprising the steps of:

(S1) uniformly mixing epoxy resin, epoxy POSS, a curing agent, a curing accelerator and auxiliary materials, grinding and defoaming to obtain a resin matrix;

and (S2) adding a diluent and a conductive filler into the resin matrix obtained in the step (S1), and continuously grinding until the fineness of the mixture reaches the requirement to obtain the conductive adhesive.

Further, the grinding is carried out in an agate mortar for 10-30min; the defoaming treatment is to defoam for 0.5-1h under the vacuum degree of 0.01-0.1 MPa.

Further, the mixture is ground in the step (S2) to a fineness of 3 to 10. Mu.m.

Drawings

FIG. 1 is a photograph showing the adhesion failure mode of the conductive paste obtained in example 1 to a copper substrate at 260 ℃;

FIG. 2 is a photograph showing the adhesion failure mode of the conductive paste obtained in comparative example 1 to a copper substrate at 260 ℃;

FIG. 3 is a photograph showing the adhesion failure mode of the conductive paste obtained in comparative example 2 to a copper substrate at 260 ℃;

fig. 4 is a photograph showing the adhesion failure mode of the conductive paste obtained in comparative example 3 to a copper substrate at 260 ℃.

Detailed Description

In the embodiment of the invention, the terminal hydrogen poly (dimethyl polysiloxane) is purchased from the chemical industry priority company of Hubei Heng Jing Rui, and the number average molecular weight is 1560, 2200, 3000 and 3800 respectively. The maleic anhydride modified liquid polybutadiene is

MA-75; anti-settling agent fumed silica is purchased from +.A.A. of Yingchuang, germany>

R-974, conductive filler silver coated plastic particles purchased from CONPART, norway, under the designation Ag-401 (G1), particle size D50 of about 5 μm; the coupling agent gamma-glycidoxypropyl trimethoxysilane was KBM-403E manufactured by Xinyue chemical Co., ltd.

Preparation example 1

0.1mol of 2,3,6, 7-tetrahydroxy-1, 10-dimethyl anthracene is dissolved in 80mL of isopropanol, the temperature is raised to 85 ℃ under the condition of reflux, 1.7mol of epichlorohydrin is slowly added in 1h for reaction for 8h at 85 ℃, the temperature is reduced to 60 ℃,10 g of 40wt% NaOH aqueous solution is added for continuous reaction for 1h at 60 ℃, 7g of 40wt% NaOH aqueous solution is added for continuous reaction for 1h at 60 ℃, 5g of 40wt% NaOH aqueous solution is added for continuous reaction for 2h at 60 ℃, the solvent and the excessive epichlorohydrin are removed by reduced pressure distillation, and the product is obtained by drying:

yield 92.1%, hereinafter referred to as A1.

Preparation example 2

Other conditions and operations are the same as in preparation example 1, except that 2,3,6, 7-tetrahydroxy-1, 10-dimethylanthracene is replaced with an equimolar amount of tetra- (4-hydroxystyrene) ethylene, to finally produce the product:

the yield was 88.6%, hereinafter referred to as A2.

PREPARATION EXAMPLE 3-1

Hydrogen terminated poly (dimethylsiloxane) of number average molecular weight 1560 (n about 20) and maleic anhydride in a molar ratio of 1:2.2 feeding, adding chloroplatinic acid with 0.5 weight percent of end hydrogen poly (dimethyl siloxane) as a catalyst, reacting for 24 hours at 80 ℃ in nitrogen atmosphere, and decompressing and rectifying to remove solvent and excessive maleic anhydride to obtain viscous liquid, namely a product:

hereinafter referred to as B1-20 (n is 20).

The number average molecular weights 2300, 3000, 3800 of the hydrogen terminated poly (dimethylsiloxane), respectively, and maleic anhydride were also used as starting materials, respectively, to give the products of formula (B1) having n of about 30, n of about 40, and n of about 50, designated B1-30, B1-40, and B1-50, respectively, according to the methods described above.

Preparation example 4

The other conditions were the same as in preparation example 3, except that hydrogen terminated poly (dimethylsiloxane) having a number average molecular weight of 2300 was used as a raw material to react with norbornylene dianhydride, and the molar ratio of hydrogen terminated poly (dimethylsiloxane) to norbornylene dianhydride was 1:2.2 feeding to give a product of formula (B2) with n about 30:

designated as B2-30.

Example 1

(S1) 15 parts of a cyclic epoxy resin (a mixed epoxy resin of a phenolic epoxy resin F51, a bisphenol A epoxy resin E43 and a tetrafunctional epoxy resin A1 obtained in preparation example 1 in a mass ratio of 15:10:5), 4 parts of a cage type epoxy resinEight (2, 3-epoxypropoxypropyl) POSS,6 parts of anhydride curing agent (tetrahydrophthalic anhydride, liquid polybutadiene modified by B1-20 prepared in preparation example 3

MA-75 according to the mass ratio of 5:10: 4), 0.7 part of 2-ethyl-4-methylimidazole, 0.1 part of anti-settling agent ∈>

R-974,0.2 parts of a coupling agent KBM-403E, uniformly mixing, grinding for 10min under an agate mortar, and carrying out defoaming treatment for 10min under the vacuum degree of 0.05MPa to obtain a resin matrix;

(S2) adding 10 parts of diluent (the compound of the trimethylolethane triglycidyl ether and the ethylene glycol diglycidyl ether according to the mass ratio of 1:1) and 50 parts of conductive filler silver-coated plastic particles into the resin matrix obtained in the step (S1), and continuously grinding until the fineness of the mixture reaches 3 mu m to obtain the conductive adhesive.

FIG. 1 is a photograph showing the adhesion failure mode of the conductive paste obtained in example 1 to a copper substrate at 260℃and illustrates 100% cohesive failure.

Example 2

The other conditions were the same as in example 1 except that 6 parts of the acid anhydride curing agent was tetrahydrophthalic anhydride, and B1-30, maleic anhydride-modified liquid polybutadiene prepared in preparation example 3

MA-75 according to the mass ratio of 5:10:4, namely, B1-20 of n=20 is replaced by B1-30 of n=30 of equal mass.

Example 3

The other conditions were the same as in example 1 except that 6 parts of the acid anhydride curing agent was tetrahydrophthalic anhydride, and B1-40, maleic anhydride-modified liquid polybutadiene prepared in preparation example 3

MA-75 according to the mass ratio of 5:10:4, namely, B1-20 of n=20 is replaced by B1-40 of n=40 of equal mass.

Example 4

The other conditions were the same as in example 1 except that 6 parts of the acid anhydride curing agent was tetrahydrophthalic anhydride, and B1-50, maleic anhydride-modified liquid polybutadiene prepared in preparation example 3

MA-75 according to the mass ratio of 5:10:4, namely, B1-20 of n=20 is replaced by B1-50 of n=50 of equal mass.

Example 5

The other conditions were the same as in example 1 except that 6 parts of the acid anhydride curing agent was tetrahydrophthalic anhydride, and B2-30, maleic anhydride-modified liquid polybutadiene prepared in preparation example 4

MA-75 according to the mass ratio of 5:10:4, namely, B1-20 of n=20 is replaced by B2-30 of n=30 of equal mass.

Example 6

(S1) 15 parts of a cyclic epoxy resin (a mixed epoxy resin of a phenolic epoxy resin F51, a bisphenol A epoxy resin E43 and a tetrafunctional epoxy resin A2 prepared in preparation example 1 in a mass ratio of 15:10:5), 4 parts of a cage type octa (2, 3-glycidoxypropyl) POSS,6 parts of an acid anhydride curing agent (tetrahydrophthalic anhydride, B2-30 prepared in preparation example 4, maleic anhydride-modified liquid polybutadiene)

(S2) adding 10 parts of diluent (the compound of the trimethylolethane triglycidyl ether and the ethylene glycol diglycidyl ether according to the mass ratio of 1:1) and 50 parts of conductive filler silver-coated plastic particles into the resin matrix obtained in the step (S1), and continuously grinding until the fineness of the mixture reaches 5 mu m to obtain the conductive adhesive.

Example 7

The other conditions were the same as in example 6 except that 15 parts of the cyclic epoxy resin was a novolac epoxy resin F51, a bisphenol A epoxy resin E43 and a tetrafunctional epoxy resin A2 prepared in preparation example 1 were prepared in a mass ratio of 20:15:6, a mixed epoxy resin.

Example 8

The other conditions were the same as in example 6 except that 15 parts of the cyclic epoxy resin was a novolac epoxy resin F51, a bisphenol A epoxy resin E43 and a tetrafunctional epoxy resin A2 prepared in preparation example 1 were prepared in a mass ratio of 15:10:2, a mixed epoxy resin.

Example 9

The other conditions were the same as in example 6 except that 15 parts of the cyclic epoxy resin was a novolac epoxy resin F51, a bisphenol A epoxy resin E43 and a tetrafunctional epoxy resin A2 prepared in preparation example 1 were prepared in a mass ratio of 15:10: 10.

Example 10

The other conditions were the same as in example 6 except that 6 parts of the acid anhydride curing agent was tetrahydrophthalic anhydride, and B2-30, maleic anhydride-modified liquid polybutadiene prepared in preparation example 4

MA-75 according to the mass ratio of 10:15: 7.

Example 11

MA-75 according to the mass ratio of 5:7:4, compounding.

Example 12

The other conditions were the same as in example 6 except that 6 parts of the acid anhydride curing agent was tetrahydrophthalic anhydride, and B2-30 obtained in preparation example 4 was modified with maleic anhydrideLiquid polybutadiene of nature

MA-75 according to the mass ratio of 5:20:4, compounding.

Comparative example 1

The other conditions were the same as in example 6 except that 15 parts of the cyclic epoxy resin was a novolac epoxy resin F51, and a bisphenol A epoxy resin E43 was prepared in a mass ratio of 15:10, i.e. without the addition of the tetrafunctional epoxy resin A2.

FIG. 2 is a photograph showing the adhesion failure mode of the conductive paste obtained in comparative example 1 to a copper substrate at 260℃and illustrates the mixed failure.

Comparative example 2

Other conditions were the same as in example 6 except that no cage type octa (2, 3-glycidoxypropyl) POSS was added, and the amount of the epoxy resin was increased from 15 parts to 20 parts. FIG. 3 is a photograph showing the adhesion failure mode of the conductive paste obtained in comparative example 2 to a copper substrate at 260℃and illustrates interfacial failure.

Comparative example 3

The other conditions are the same as in example 6, except that 6 parts of the anhydride curing agent are tetrahydrophthalic anhydride and maleic anhydride-modified liquid polybutadiene

MA-75 according to the mass ratio of 5:4, compounding. I.e., without adding the B2-30 prepared in preparation example 4. FIG. 4 is a photograph showing the adhesion failure mode of the conductive paste obtained in comparative example 3 to a copper substrate at 260℃and illustrates the mixed failure.

Application example

The conductive pastes obtained in the above examples and comparative examples were subjected to the following performance tests, and the results are shown in table 1.

Conductivity test: the test was performed with reference to ASTM D257.

Storage modulus test: the test was performed with reference to astm d4065 standard.

Adhesion to copper substrate test: a2 x 2mm silicon chip was mounted on a copper frame and cured under conditions of elevated temperature from 25 ℃ to 175 ℃ for 30 minutes and then held at 175 ℃ for 60 minutes and cured in an oven. After curing, the shear strength of the wafer at 25℃and 260℃was measured using an automatic adhesion measuring device, respectively.

TABLE 1 conductive adhesive Performance test results

As can be seen from the data in Table 1, the single-component semiconductor conductive adhesive prepared by the invention has excellent comprehensive performance, good conductivity, lower storage modulus, excellent high temperature resistance and damp-heat resistance. As can be seen from comparison of examples and comparative examples, the conductive adhesive of the invention can achieve satisfactory degree in all performance indexes simultaneously by specific selection of each component, in particular to multi-functional fused polycyclic epoxy resin in epoxy resin, epoxy POSS and compounding of curing agent with end group as acid anhydride and side chain as acid anhydride in curing agent.

Claims

1. The single-component conductive adhesive for the semiconductor is characterized by comprising the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 4-8 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 5-10 parts of diluent;

the epoxy resin comprises phenolic epoxy resin, bisphenol epoxy resin and polyfunctional condensed polycyclic epoxy resin; the epoxy value of the phenolic epoxy resin and the bisphenol epoxy resin is 0.4-0.6, and the functionality of the polyfunctional condensed polycyclic epoxy resin is 3-6;

the anhydride curing agent comprises a small-molecule anhydride curing agent and a high-molecule anhydride curing agent, wherein the small-molecule anhydride curing agent is at least one selected from maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, dodecenyl succinic anhydride and 4-methylhexahydrophthalic anhydride; the macromolecular anhydride curing agent comprises polysiloxane with acid anhydride as a terminal group and maleic anhydride modified liquid polybutadiene; the polysiloxane with the end group being anhydride has the structure of at least one of the following formulas (B1), (B2) and (B3):

、

、

；

wherein R is ₁ Independently selected from H and methyl.

2. The conductive paste for single-component semiconductors according to claim 1, wherein the epoxy group POSS has a chemical structure represented by the following formula (I):

；

each R is independently 2, 3-glycidoxypropyl, 3, 4-epoxycyclohexylethyl.

3. The conductive paste for single-component semiconductors according to claim 1, wherein the mass ratio of the novolac epoxy resin, the bisphenol epoxy resin and the polyfunctional condensed polycyclic epoxy resin is 15 to 20:10-15:3-6.

4. The one-component semiconductor conductive paste as claimed in claim 3, wherein the polyfunctional condensed polycyclic epoxy resin is selected from the group consisting of:

、/>

、

at least one of (a) wherein A is +.>

Represents a site of attachment to a phenyl group, R is independently selected from H, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl.

5. The conductive adhesive for single-component semiconductors according to claim 1, wherein the curing agent is a small molecule anhydride curing agent, polysiloxane with an anhydride end group, and maleic anhydride modified liquid polybutadiene, and the mass ratio is 5-10:10-15: 4-7.

6. The conductive paste for single-component semiconductors according to claim 1, wherein the diluent is at least one selected from the group consisting of t-butylphenyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and o-tolyl glycidyl ether;

the conductive filler is selected from silver powder, silver-plated copper powder, silver-plated nickel powder and gold powder; the conductive filler is spherical powder, flaky powder or dendritic powder, and has a particle size of 0.1-10 μm;

the curing accelerator is imidazole curing accelerator.

7. The conductive paste for single-component semiconductors according to claim 6, further comprising 0.05 to 0.2 parts of an anti-settling agent, and 0.1 to 0.5 parts of a coupling agent;

8. The conductive paste for single-component semiconductors according to claim 6, wherein the imidazole-based curing accelerator is at least one selected from the group consisting of 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.

9. The method for preparing the conductive adhesive for single-component semiconductors according to any one of claims 1 to 8, comprising the steps of:

10. The preparation method according to claim 9, wherein the grinding is performed in an agate mortar for 10 to 30 minutes; the defoaming treatment is to defoam for 0.5 to 1 hour under the vacuum degree of 0.01 to 0.1 MPa; grinding in the step (S2) to make the fineness of the mixture to 3-10 μm.

11. The single-component conductive adhesive for the semiconductor is characterized by comprising the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 4-8 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 5-10 parts of diluent;

the epoxy resin comprises phenolic epoxy resin, bisphenol epoxy resin and epoxy resin shown in a formula (II); the epoxy value of the phenolic epoxy resin and the bisphenol epoxy resin is 0.4-0.6;

；

wherein A is

Represents a site of attachment to a phenyl group, R is independently selected from H, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl;

the anhydride curing agent comprises a small-molecule anhydride curing agent and a high-molecule anhydride curing agent, wherein the small-molecule anhydride curing agent is at least one selected from maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, dodecenyl succinic anhydride and 4-methylhexahydrophthalic anhydride; the macromolecular anhydride curing agent comprises polysiloxane with anhydride as a terminal group and maleic anhydride modified liquid polybutadiene; the polysiloxane with the end group being anhydride has the structure of at least one of the following formulas (B1), (B2) and (B3):

、

、

；

wherein R is ₁ Independently selected from H and methyl.