Corrosion suppressing method for electronic components

[Detailed Description of the Invention]

[Industrial Application] The present invention relates to the Serra To ivy board, a substrate for electronic devices like a glass substrate, and the printing circuit board that has one or more electronic devices. [Description of the Prior Art] A semiconductor device and an electronic device like an integrated circuit are attached on various substrates. These substrates contain not only a printing circuit board but the ceramic substrate and glass substrate which can be made, for example from polymer material. In order to protect a device and the connected wiring from the surrounding contamination, a substrate and an electronic device are sealed. Sealing of a package is protected also from the process residue by which the trap was carried out. An example of the seal package is described by United States patent 3.993rd and No. 123. However, the present invention relates mainly to a non-sealing package (it is applicable also to a seal package). In this case, since electronic component parts (a substrate or an electronic device) are made still unreserved, it is comparatively easy to be polluted from the circumference. Then, encapsulation of the electronic component parts can be carried out, or they can also be covered and protected by another method. However, the protection performed by a cover layer (it is a surface protection film in practice) is not perfect. Since even the best encapsulation material makes the surrounding gas-like impurities penetrate, there is a limit also in the protection to the invasion, and it cannot protect from the process residue by which the trap was carried out at all. Added the complexing agent to such materials, the ion contaminant and the complex were made to make in consideration of the fault of encapsulation and the material of cover, and removing the harmful influence of an ion contaminant has been proposed. It is common knowledge for sodium, potassium, and an ion contaminant like chlorine to react to metallurgy (metallurgy) which is not protected, to start corrosion and electrophoresis, and to degrade perfect electronic component parts. Some of these ion contaminants exist originally in encapsulation and the material of cover. Another ion contaminant originates in the material to which it adheres into the process of electronic component parts, and a trap is caught and carried out to the fine pores and the hollow in a package. The art of making the problem of the ion contaminant in encapsulation material reducing is indicated by United States patent 4,271*No. 425, the 4th, and No. 3L6,796. This patent has proposed mixing crown ether (croiyn ether) or cryptate ether (cryptate ether) into encapsulation or the material of cover. Since such a complexing agent is added in encapsulation or the material of cover, they from the position of a substrate and a device which other ion contaminants generate become far. Therefore, the effect that these ion contaminants prevent the corrosion reaction which becomes a cause and occurs is restricted. In order that such an ion contaminant may remove, encapsulation or before covering, it is generally ineffective to wash a package simple. Crown ether and cryptate ether are known as a complexing agent as indicated to the above-mentioned United States patent. In existence of sodium, United States patent No. 4.711.853 has described extracting potassium from the solution containing crown ether alternatively. - The capability for crown ether to extract the ion of alkali and alkaline-earth metals to boat fishing is accepted by this technical field, It has been reported by the Americanization study academic journal (J, American ChemicalSociety;by Pedersen, C, J, 89.7017.1967 years). Similarly, the capability for cryptate ether to make a positive ion and negative ion, and a complex has been reported by "Indenter J (Endeavour Hby Truter\ 30 or 142.1971 years), for example. Cribbutate ether and crown ether can be classified into Genus of a crown compound. A productive operation on the characteristic which makes crown compounds and those complexes, "Crown compounds, those characteristics, and application (Crown Compounds, their characteristics andapplications)" (by Michio Hiraoka.) It is described in Elsevier 5 cientific Publishing Company and NewYork 1982. In spite of knowing from before using the characteristic that a crown compound makes a complex, and them for the encapsulation material of an electronic device, the necessity of improving the corrosion prohibitive power in a package is left behind. [Problem(s) to be Solved by the Invention] An object of the present invention is to improve control of the corrosion in a package. The present invention aims at control of the corrosion in the package by an easy and effective method. [Means for solving problem] The object of the present invention is achieved by inventing the inhibition method of the corrosion in electronic component parts. It is the method of specifically washing electronic component parts with the solution consisting of a crown compound. [Example] According to the present invention, the inhibition method of the corrosion in electronic component parts is indicated. The method consists of a process of washing a, the process of obtaining electronic component parts, To, and the electronic component parts, in the solution consisting of the solvent which a crown compound complexing agent and the above-mentioned complex compound dissolve. A crown compound complexing agent is chosen from the group which consists of crown ether, cryptate ether, and its mixture. A crown compound is common knowledge at the person skilled in the art of this field. The capability to extract those positive ions and negative ion is also common knowledge. The crown compound to be used is decided by many factors, such as special application which poses a problem, for example, ionic species by which a trap is carried out, heat stability, and a solvent used. It should evaluate that the present invention has many loun compounds in use Possible. Selection of the specific crown compound to be used will be understood by instruction of the following present invention. Generally, in making a positive ion (for example, sodium or potassium) and a complex, it chooses crown ether. On the other hand, cryptate ether is preferred when making negative ion (for example, chlorine) and a complex. This is not a rule which is not changed so that it may be recognized by the person skilled in the art. choosing crown ether, in order to make specific negative ion and complex so that it may be clarified from now on -- a positive ion specific on the other hand -- cryptate ether Choose -- things are also made. There is crown ether of three models which are related to the present invention. That is, it is ring type oligomer of alicyclic crown ether, aromatic series crown ether, and ethylene oxide. As an example of alicyclic crown ether, it is Xanaw 1 and 47 to 2.3, 11, and 12. Dicyclo. 10 13 16 hxaoxa cyclo Octadecane is raised and it is expressed by the following structure. The vernacular name of this crown ether is dicyclohexyl 18-crown 16 crown ether. For clarification and facilitation, a vernacular name is often used on these specifications. It is not limited although dicyclohexyl 24-crown 8 crown ether and dicyclohexyl 30-crown 10 crown ether are raised as another example of alicyclic crown ether. As an example of aromatic series crown ether, it is dibenzo 18-crown~6. Crown ether (2, 3, 1112-dibenzo 1, 4, 7, 10, and 13, 16-hxaoxa cyclo Octadeca- 2 and 11, Diene) is raised, and it is expressed by the following structure. Although dibenzo 24-crown 8 crown ether and dibenzo 12-crown 4 crown ether are raised as another example of aromatic series crown ether, it is not limited to these. As an example of ring type oligomer of ethylene oxide, 18 crown 6 (it is Kisaoxasi cloakroom TADECAN to 1, 4, 7, 10, 13, and 16) crown ether is raised, and it is expressed by the following structure. Although 5-crown 5 (1, 4, 7, 10, 1, 3-Pentaoxa cyclo Pentadecane) crown ether and 12-crown 4 (1, 4, 7, 10 tetraoxa cyclo Dodecane) crown ether are raised, it is not limited to these. Crown ether is a Aldrichski chemical corporation (Aldrich Chemical Company; Milwaukee.) easily. A help can be carried out from Wiscons in. The crown ether of alicyclic and an aromatic series is preferred for the object of the present invention among these crown ether. Since ring type oligomer (for example, 18-crown 6) of ethylene oxide is water solubility, it is not usually preferred for the object of the present invention. If it says simply, without bringing up a special theory, it will be understood that it is for the residue of crown ether to remain after the reason the present invention is very effective washes electronic component parts. This crown ether has served to catch the isolation ion contaminant after washing process completion for a long time. Crown ether is exposed to the humidity in the air as crown ether is water solubility, and it decomposes in the 0 It was case, therefore loses the effect. However, in spite of being water solubility, many these water-soluble crown ether is used. Therefore, these are included in the range of the present invention. Among the crown ether of alicyclic and an aromatic series, since alicyclic crown ether is excellent in heat stability, it is clearly preferred. Electronic component parts are covered over the process and the use, or its either at a high temperature after washing in many cases. Therefore, supposing the residue of crown ether remains on the surface of electronic component parts, the heat stability will pose a problem. It was found out that the most desirable alicyclic crown ether is Xyl 18-crown 6 crown ether in Dicyclo. Since today's electronic component parts are covered over many processes before they are attached, they will introduce impurities into electronic component parts. It is more desirable to perform washing of these electronic component parts after such a process. Only 1 time of a washing process may be sufficient as washing of the electronic component parts according to the present invention, or even if it uses two or more times of washing processes, it is not cared about. The washing process of following the present invention is not limited only to the situation where an ion contaminant is introduced into electronic component parts. It was found out that the present invention is effective also in washing of the electronic component parts exposed to the unclean solvent. The quantity of the complexing agent added by the solvent is decided by three factors. That is, it is the solubility to a price, the impure amount of resources, and a solvent. The maximum quantity of a complexing agent is restricted by the solubility to a solvent. In other words, it is dependent on the complexing agent and solvent to be used. As for a complexing agent, if a price is taken into consideration, it is preferred to use the minimum quantity as much as possible. The minimum quantity is sufficient quantity which has as much as possible little quantity of the complexing agent to add to make all the isolation ion contaminants and complexes. Specifically, the molar quantity of a complexing agent adds to the extent that it becomes equal to the molar quantity of an isolation ion contaminant at least. In fact, the molar quantity of a complexing agent is added about 3 times as much as the molar quantity of an isolation ion contaminant. If there is a quantity like this, a washing process can be performed certainly. 2 Both of the organic solvents, polarity and non-polarity, are suitable for the crown ether of alicyclic and an aromatic series. As an example of polar solvents, a Te 1-La hydro franc (THF), Grimm (1, 2-dimethoxyethane), and a jig rim (diethylene glycol dimethyl ether) are raised. As an example of a nonpolar solvent, there are acetonitrile, xylene, benzene, hexane, and toluene. Desirable solvents are T HF and xylene. And these mixtures can also be used. In the present invention, it was found out using the separation solution consisting of the solvent of polarity and non-polarity that it is effective to wash the surface of electronic component parts. Thus, the process of following the present invention removes a process residue more effectively. Cribbutate which is in the present invention at a relation is Cribbutate of a monocycle type and a polycyclic type. As an example of monocycle type cryptate, 1, 7, 10.16-tetraoxa 4, and 13-Diazoshi cloakroom TADECAN are raised, and it is expressed by the following structure. 3 This monocycle type cryptate is fatty series aza-crown ether. As another example of monocycle type cryptate, aromatic series aza-crown ether, alicyclic ether, and heterocyclic aza-crown ether are raised. As an example of polycyclic type Cryptand (sometimes, called Cryptand (cryp tand)), 4, 7 *13.16.21-pen Tao A kiss- 1, and 10-diazabicyclo (8, 8, 5) Rico Sun are raised, and it is expressed by the following structure. It is run ether. As another example of polycyclic type Cryptand, tricyclic crown ether, spherical Cryptand, and 2 ring type aza-crown ether and negative ion Cribbutate are raised. Cribbutate is sold by a name of article called crypto Fix (Kryptofix) from EM Saiensu-Sha (EMScience; Cherry 1ltll, New Jersey). A help can be carried out easily. Compared with crown ether, cryptate has stronger ion selectivity and bigger complex stability, and catches a metal ion firmly to the space in a lattice. Generally, the polycyclic type Cribbutate can form a stable complex rather than observed by monocycle type Cryptand. Generally, the dissociation rate of cryptate is smaller than the dissociation rate of the complex of crown ether. That is, this shows that cryptate is more nearly thermodynamically [ than a crown ether complex ] stable. The capability to make the transition metal of cryptate and a complex with a heavy metal ion is superior to corresponding Crown Ey Chill's capability. Although Kribachi- 1- dissolves in water and the organic solvent, all cryptates do not dissolve in water. Water-soluble Cryptand can be used for the present invention. It is because these will not necessarily be decomposed into humidity like water-soluble crown ether. The organic solvents which can be used are ethanol, Methyla linen, a jig rim, THF, diethylether, and methanol, for example. And these mixtures can also be used. Unlike crown ether, the solution containing Cribbutate and the solvent of polarity or non-polarity is uniform, and acts effectively. The quantity of the cryptate added by the solvent is decided by a factor which was before stated about crown ether. It may be found out that it is effective to mix cryptate and crown ether in one solution. As long as a common solvent is used, such solution acts satisfactorily. Other combination of a crown compound is possible. 6- Other specific crown compounds which are not described, for example, thia crown ether, ring type aza-thia ether, and aza-thia crown ether are effective in this specification in order to make other negative ion and positive ions, and complexes. It is contained in the range of such other crown compound mist beam present invention. It is sure that the method of following the present invention is widely applicable to many various models and the electronic component parts of a kind. For example, electronic component parts are a semiconductor chip or an electronic device like an integrated circuit. Electronic component parts are substrates like a ceramic substrate (for example, alumina), a glass substrate (for example, borosilicate glass), or glass/ceramic substrate (for example, Cordierite). Even if it combines some of these electronic component parts, it is applicable to a process. Electronic component parts can be covered using an existing damp-proof material like elastomers which polymerized, such as RTV silicon currently indicated according to the present invention, for example by above-mentioned United States patent 4th, No. 27L425, and No. 4,396,796. An existing damp-proof material contains the complexing agent of 7-crown compound. Since it cannot protect completely only with an existing damp-proof material so that it may be clarified below, an existing damp-proof material is rather added to the present invention. The point which is excellent in the present invention will be clarified by the following examples. Example 1 A series of samples were prepared. Each sample consisted of a multilayer ceramic Al To do board, and had the metallurgy of nickel on it. Some samples were made to pollute with doping solution intentionally. And the sample was dipped in the separation solution of THF and xylene in which Xyl 18-crown 6 crown ether (CE) is added by some to Dicyclo. Then, the sample was dried. Some samples were covered by the polyisobutylene (PIB-1-CE) which contains Xyl 18-crown 6 crown ether to polyisobutylene (P I B) or 0.1% of the weight of Dicyclo. And all the samples were covered and it sealed. l 8- In order to examine the corrosiveness-proof of a sample, the environmental test for L OO 0 hour was done, having applied DC bias voltage of 10V on condition of 85 degreeC/80% relative Moist temperature. A test result is as in Table I. Table I Hinamori Utago songs overflowing message A dark Nod 4 Factory-Losing 05m1 (CE[ CI- -CE-less ]-less PIB+GE Yes and 05mIC1,002mCE) Nothing [ 002 mCE PIB+CE ], OLmHCI CE[ CE-less ]-less PIB Yes, 01mtlCI, 05mCE, nothing [ 05mCE PIB ], and 01mMCl , 05mCE Nothing [ 05mCE non-], CE[ 01-mNaOHCE-less ]-less PIB+CE Yes, 01mNa011.05mCE, nothing [ 05mCE PIB ], 01mNa0t+ 05mCE '05mCE -less non-heat CE[ CE-less ]-less PIB non-heat 05n+CE, 05mCE PIB non-heat 05mCE 05mCE PIB non-heat CE[ CE-less ]-less PIB+GE Existence 05mCE 05mCE 'PIB+CE Non-heat 05mCE 05mCE Since corrosion takes place from a PIB+CE free-of-examination result when it washes using the solution which does not add a complexing agent, Washing of the sample according to the present invention effective in preventing the attack of ion is clear. It turned out that this result is applied also about the sample which has covered the surface by PIB, and it gives protection with the suitable present invention. Example 2 A series of another samples were prepared. Each sample consisted of multilayer Serra Kutsuku alumina substrates, and had the metallurgy of nickel on it. All the samples were dipped for 30 minutes into doping solution. Then, the sample of Okay. was dipped between IO parts into the washing solution made to agitate with constant speed. The part of those washed samples was dipped in the separation solution of THF and xylene in which Xyl 18-crown 6 ether (CB) is added by some to 0.05-mol Dicyclo. Other samples were dipped in 0 or 05-mol cryptate solution. A solvent is either water or methanol and is Ah 0. Ivy. Used cryptate, They are crypto Fix 22 or (L 7.10. 16-Citraoxa 4 *13-diaza cyclo Octadecane) (4, 7, 13, 16, 21-pen Tao A kiss- 1, 1, and 0, - diazabicyclo [8 *8.5) crypto Fix 221 Rico Sun. Each future is referred to as cryptate 1 and cryptate 2. The cryptate and crown ether of a grade or the molar quantity beyond it in which ion concentration is neutralized were added to the washing solution. All the samples were dried after washing and the environmental test for 720 hours was done on condition of 85 degreeC/80% relative humidity. A test result is as in Table ■. Table 2 Hi 05-m1IC Q5mHC ,0,5mtlC Q5mHC ,05mHC It is as bare feet Liquid exsolution. - Nothing THF/xylene TIIF / xylene / GE Chrysotate 1 (Wed.) Cribbutate 1 (methano 10) 1 05-m1+C1 Crib ?-2 (Wed.) Nothing, 05mMCl Nothing [ Cribbutate 2 (methanol) ], nothing [ 05mNaC1 ] Yes 05mNaCl TIIF/xylene Xile: [ Yes 05mNaClTHF / ]//CB Nothing, 05mNaC1 Cribbutate 1 (Wed.) Nothing, 05mN, icI Cribbutate 1 (methanol) Nothing, 05mNaC1 cryptate 2 (Wed.) Nothing, 05mNaC1Cribbutate2(methano)1 Nothing, 05mNa0II Nothing Yes 05mNaOHTIIF / xylene Yes 05mNaOHTl (F / xylene / CE) Nothing, 05mNa01l. Cribbutate 1 (Wed.) Nothing, 05mNaOH Cribbutate 1(methano 11)1 duties, 05mNa011 Cribbutate 2 (Wed.) Nothing, 05mNa01+ Cribbutate 2 (methanol) It was checked that, as for the sample washed only by the sample or T HF, and xylene which are not washed, the corrosion of the metallurgy of nickel takes place from a free-of-examination result. It is Including 2 about crown ether or Cribbutate. Not corroding the sample washed by Solution was found out. [Effect of the Invention] The present invention can provide the method of controlling the corrosion in electronic component parts.