DE2339607A1 - METAL DEPOSITATION METHOD - Google Patents

Description

BLUMBACH ■ WESER · BERGEN & KRAMER

PATENTANWÄLTE INWIESBADEN AND MUNICH 2 3 3 9 R Π

DIPL-ING. P. G. BLUMBACH · DIPL-PHYS. Dr. W. WESER DIPL-ING. DR. JUR. P. BERGEN DIPL-ING. R. KRAMER

62 WIESBADEN SONNENBERGER STRASSE 43 TEL (06T21) 562943, 561998 MDNCHEN

WESTERN ELECTIiIC COMPANY Lando 4

Incorporated

NEVv YORK, N.Y. 10007 United States

Process for depositing a metal

The invention relates to a method of electroless deposition of a metal on a surface of a non-conductive substrate

It is now known to produce metallic patterns on electrically non-conductive substrates. These patterns can be used as electrical circuits, decorative arrangements, or the like. Metallic patterns can be made by many methods. Particularly important among these methods are the electroless plating, which involves electroplating the electrolessly formed

409809/1086

Musiers can connect, involve in the course of the proceedings. In a typical process for electroless medashing from TUetall * at least one surface area becomes a Sensitized non-conducting substrate. Sensitizing takes place by applying a Sensibilisa.orlösung, z. s.

ZinnttD tiloride, on the surface area, which has an activating

+2
Meiallion, e.g. ^:> . Pd, into an activating me.all, e.g. 3. Pd, can reduce. The serisibilized part of the surface is then in an Ak ivierungslösung with an activating ivle.allalz, for example PdCl, immersed, in the activating metal, for example

German

Pd is reduced on the surface area mentioned. The surface with activating metal in the reduced state is then subjected to a conventional bath for electroless formation exposed to a metal blow.

An additional electroless plating method is the method described in patent application P 19 17 474.4-45 phoiosele '-. iven knockdown of Me, all. Here are the Pattern made without etching or masking the Phoolaekes. On the substra. is specially a "photopromoter"

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called solution applied, which (or at least a part of the) is adherent there. The attached photopromoter has a species that has an Ox> dation state can change if it is exposed to appropriate radiation. In a state of oxidation (but not in both) the photopromoter species can be a precious metal (defined as palladium, platinum, gold, silver, osmium, indium, Iridium, Rhenium, Rhodium) from its salt solution. The precious metal conducts an autocatalytic, currentless running Flattening method.

As soon as some photopromoter sticks to the substrate surface, it becomes they are exposed to suitable radiation, especially short-wave ultraviolet radiation less than 3000 Å. To this Irradiation can reduce the precious metal in some parts of the substrate surface, while others do not. Then the metal is de-energized only depressed where it is desired, d. h, on the reduced precious metal.

If the substrate to be provided with a metal pattern is water- is repulsive, as z. B. the case with substrates made of organic polymers, it is very often difficult to sensitize it with aqueous

4 09809/1086

To wet solutions (conventional, "electroless metal deposition"). Also, it is sometimes difficult to come up with a practical one with some possible photo promoters (photoselective metal deposition) To achieve wetting effect. The practical wetting effect is defined as the ability of a surface to act on an essentially microscopically smooth, ground surface part of the same a coherent, thin, and even layer of a Liquid such as water or some other liquid medium to form when the surface is vertical or in any other position is held.

With it a water-repellent surface with aqueous sensitizing solutions can be wetted, the water-repellent surface becomes with conventional, electroless, metal deposition processes usually roughened first (either mechanically or chemically) before applying the sensitizing solution is applied. However, roughening has the disadvantage that the resolving power of the resulting electroless metal deposit becomes less.

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23396Q7

It is therefore desirable to enable a better or practically feasible wetting of a water-repellent surface, which is to be subjected either to a conventional, electroless metal deposition process or to the photoselective metal deposition process mentioned above in patent application P 11474.4-45, without the surface being roughened or roughened is pickled. Ee is further desirable to improve the already superior adhesion properties in itself of the metal layers, which are prepared by the in patent application P metal deposition process described 19 17 474.4-45.

In addition, it was found that aqueous solutions of conventional sensitizers and photopromoters only act as a sensitizer for a short time. Photo promoters work and therefore cannot be kept for future use. Therefore, a stated goal is to produce long-lasting sensitizer * and / or photopromoter solutions.

The invention relates to a method for electrolessly depositing a metal on a surface of a non-conductive one

409809/1086

Substrates. In a first embodiment, a suitable substrate is used

first sensitized with a sensitizer that is known to

+2 + ^ +2 +1

sizing species e.g. B. Sn, Ti, Pb, Hg ions, etc. contains and which a suitable organic solvent, e.g. B. Acetone, liquid phenol, acetic acid, methyl ethyl ketone, tetrahydrofuran, dimethylformamide and mixtures thereof are added is. The sensitized substrate is then activated by it a suitable activation solution, e.g. B. a PdCl solution containing ions is exposed. The activated substrate will then placed in a conventional bath so that an electroless metal precipitate forms on it «

In a second embodiment of the present invention, a suitable substrate is first coated with a solution that contains Sn ⁺² , Ti ⁺³ , Pb ⁺² , Hg ⁺² , Fe ⁺⁸ as photopromoter species and with a suitable organic solvent, such as z. B. acetone, liquid phenol, acetic acid, Meth.lathylketon, tetrahydrofuran, dimethylformamide and mixtures thereof is added.

409809/1081

The substrate coated with the photopromoter is then irradiated with ultraviolet radiation of short wavelength to produce a Manufacture patterns of the photopromoter that reduce a precious metal such as Pd from a precious metal salt such as PdCl can. The irradiated substrate is then immersed in a solution with a salt of the noble metal in order to be absorbed by chemical reduction To form patterns from such a precious metal. Finally, the precious metal pattern can be used as a catalyst to put a metal on it, e.g. Copper to produce a metallic pattern in an autocatalytic, electroless plating bath. The metal pattern can be used as a circuit pattern for a circuit substrate.

The following drawings will facilitate understanding of the invention in conjunction with the specific one below Description. The drawings show:

Fig. 1 is a partial perspective view of a substrate

with a surface on which there is a photopromoter layer located, and

4098Q9 / 1086

FIG. 2 is a partial perspective view of the FIG

Fig. 1 shown substrate, on that according to the novel method according to the invention a metal must he was put down by photoselective means.

The present invention was primarily explained as the deposition of Pd and Cu on a surface of a non-conductive substrate, fcs is easy to see that the inventive concept is equally applicable to the deposition of other suitable metals by catalytically activating metals or noble metals (platinum group ) such as E. Palladium, platinum, gold, silver, iridium, osmium, lihenium and rhodium can be reduced from their respective ions. A suitable substrate is chosen. Those substrates are suitable for making electrical circuit patterns that are generally non-conductive. In general, all dielectric materials are suitable substrates. In a first embodiment of the invention the substrate, e.g. A polyimide, is sensitized by applying a suitable sensitizer to its surface to form a sensitizing layer or coating. The Seneibiiielerung consists of

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precipitating or absorbing a sensitizing species, e.g. B. Sn ⁺ -, Ti ⁺³ -, Pb - and Hg ⁺ ions etc., the

is easily oxidized on the substrate surface. A suitable one

"f * 2 Ί · 3 4 * 2 + I

Sensitizer is a solution with z. B. Sn, Ti, Pb, Hg ions etc. than conventional sensitizing species that are well paved and with a suitable organic solvent.

A suitable organic solvent is one which, firstly, dissolves the sensitizing species or one with it results in a compatible mixture, which secondly has a low surface energy of typically 25-45 dyne / cm, and thirdly with the selected substrate, e.g. B. polyimide, is compatible and wets its surface. Some suitable organic solvents contain acetone, phenol (which is kept at a temperature of over 43 C), methyl ethyl ketone, acetic acid, tetrahydrofuran, Dimethylformamide and mixtures of these organic solvents, with a component between 10 and 90 vol. 7 ", z. B. 10 to 90 vol. Fo Methyl ethyl ketone, the remainder acetic acid, can ingest.

A09809 / 10ÖÖ

+2 +3 +2 +1 The sensitizing species, e.g. _> n, Ti, Ib ", Hg etc.

becomes the appropriate organic solvent or wetting agent added in an amount that a concentration is established, which is typically between a minimum of 0.1 weight / », in which a selected substrate surface is sufficiently sensitized and a maximum at which the selected carrier is saturated. The concentration range is of the special _> ensi-

+2
bilization species, e.g. Jn, and their corresponding compound

z. B. SnCL. 2HO, the desired level of sensitization and the specific solvent or wetting agent chosen. Parameters such as sufficient sensitization or such as the associated concentrations of a sensitizing species are known to those skilled in the art or are readily ascertained by them through simple experimentation.

The appropriate sensitizer will appear on the surface of the substrate applied using any of the conventional methods, e.g. B. dipping, spraying, Brushing, stamping, stenciling, etc.

409809/1088

Sol oho ancestors are In the I'echnil: known and are here no further explanation · .. In this regard it should be noted that Sensitization processes as well as common sensitization species At least in part in the article "T-. I et alii c Coating of Plastics "by .Villiam Goldie, who in Löüo published in the journal "Electrochemical Publications".

Unlike other known methods for electroless ! Precipitation of metal requires the need to be sensitized No pretreatment or pickling of the substrate surface before it is sensitized with the sensitizer according to the invention The previous or pickling treatment refers to roughening (with mechanical 3 \ 'i.teln), etching, hydrolyzing, Oxidizing (by chemical means), etc. an area of a water-repellent surface, e.g. B. a polyimide surface, so that this area by common liquid mustard sensitizers (non-wetting) better wetted, and that formed on your currentless As a result, metal precipitate ultimately adheres better (perhaps associated with a loss of resolving power and / or a degradation of surface properties). Before the

409809/1086

BATH ORIGINAL

Application of the sensitizer does not require a pickling treatment, because the sensitizer has a water-repellent surface, e.g. B. a polyimide surface, sufficiently wetted, whereby the dissolution · and adhesiveness of a metal deposit B electrolessly applied to the water-repellent surface is improved target.

After the substrate surface has been sensitized, it is watered and then activated. It is important that the finish after sensitization, thoroughly in a cleaning agent,

z. B. deionized water, is watered. If that doesn't happen

+2 it is possible that an activating species, e.g. B. Fd to which the sensitized surface is to be exposed is reduced without it adhering to said surface. Ά In this regard, it should be emphasized that other than other processes for electroless deposition of metal, in which z. B. by embossing, printing, stenciling, etc. a sensitized pattern is created on the substrate surface, the rinsing of the sensitized surface with water does not cause a blurred image. On the contrary, an electrolessly formed pattern of a mead «precipitate» with very sharp details and a

409809 / 10gS

fine resolution.

When activated, a precipitate of catalytic metal, ζ. B. a noble metal such as Ir, Os, Pd, Pt, Ilh, Rd, Au ₁ Ag is formed over parts of the sensitized surface in sufficient quantity to catalytically influence a plaiting reaction as soon as the surface is in an electroless plating bath is immersed. The sensitized surface that such an activating metal, ζ. B. Pd, from an activating metal salt, e.g. B. PdCl_, can reduce the activating Me all salt, z. B. PdCl, whereby the activating metal salt into the activating metal, e.g. Being deposited gradually thereafter, Pd, is reduced. The deposited activating metal, e.g. B. Pd, acts as a catalyst for localized further plating. The various activation metal ions and their solutions, the activation conditions and methods are known and are not explained further here. Such chemical accelerators (activators) and processes can be found described in part in the article "Metallic Coating of Plastics" by William Goldie, which appeared in 1968 in the journal "Electrochemical Publication".

409809/1066 original inspected

After activation, the substrate on which the activating Me.all is deposited can be for about 1 minute at 25 C more certain.

after which it is placed in a standard electroless plating bath

+2 is immersed, which holds a Me allion, e.g. Cu, en to by a suitable reducing agent, e.g. B, formaldehyde, hydrazine, in the presence of the catalytically activating metal spikes, e.g.

♦ 2

Pd to be reduced catalytically. The metal ion, s, Ώ. Cu,

is generated by a species contained in the electroless bath, e.g. B. Formaldehyde, electrolytically reduced, as long as the activating metal, e.g. B. Pd, is present, and on the surface of the Substrate is simply knocked down as metal without the supply of electricity. The electroless baths, the plating conditions and methods in the absence of electricity are known and will not be discussed further here. It will turn to the essay "Metallic Coating of Plastics" by William Goldie, which gives some typical examples of electroless baths and plating parameters.

If it is desired to apply a further precipitate to the electrolessly formed precipitate, the electrolessly represented metal precipitate of a conventional electrical

409809/1086

ORIGINAL JNSPECTED

subjected to plating treatment by either the same or another metal is applied, which surely depends on what the deposited pattern is used for.

When a metal on the surface of a non-conductive substrate is to be selectively deposited, creating a metal pattern, a standard method can be used to to produce subtractive etching patterns. As an alternative to this, the eele'Ttive rebound can be done in the conventional way by masking procedures, applied to the substrate surface, or by selective application of the appropriate sensitizer, ζ. B. by Embossing, stenciling or printing are carried out as described in the patent application P 22 5G 960.4 by D. J. Lando.

In a broad embodiment of the invention, which is shown in FIG. 1, part of a suitable non-conductive Substrates * shown. You choose a suitable photo promoter. In the patent application P 19 17 474. 4-45 such a all is one Defines substance which, when acted upon by a suitable energy, either (a) emits chemical energy which it possesses, or '

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(b) stores chemical energy that it did not previously have. If this substance possesses or has stored chemical energy, it can act as a chemical accelerator (promoter), which behaves significantly different from a catalyst that accelerates or supports a chemical reaction. A promoter differs from a catalyst in that it undergoes a chemical change as it performs its function.

A positive photo promoter is in the Pa! en registration P 18 17 474 «4-46 defined and described as a photopromoter with a metallic photopromoter species that has two characteristic features. They are namely (1) a state of oxidation or a cyclization number which can be changed (either upwards or downwards) if the mentioned photopromoter species of radiation of a suitable wavelength (short-wave ultraviolet light of less than 3,000 A) exposes and can (2) in its original state (but not in its altered state) a precious metal ζ. B. palladium, from a solution with a salt of the noble metal, e.g. a PdCl solution.

A negative photopromoter is in the patent application P 1Θ17 474.4-46

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as a photopromoter with a metallic photopromoter species defined and described, which has two characteristic features. Namely, it has (1) an oxidation status or a Oxidation number that can be changed (either up or downwards), if one considers the mentioned photopromoter species of radiation of a suitable wavelength (short-wave ultraviolet Exposure to light less than 3000 A), and can (2) in its original state (but not in its altered state) no Udelme.all, ζ. B, palladium, from a solution with a salt of the precious metal, e.g. B, a PdCl solution.

According to the information made in patent application P 10 17 474.4-45 * guides are those photopromoters suitable as positive

+2 +3 +2

Photopromoter species contain Sn, Ti, Pb ions. Compounds of tin are generally considered to be suitable photopromoter species. TUan and lead such as B. halides, nitrates, sulfates, Oxalate, Accate, eic.

Some suitable positive phocopromoters are especially solutions of tin, titanium or conductive halides, see B * SnCl ₃ ,

409809/1086

, TiBr ₃ , PbQ ₂ , PbBr ₃ .

Suitable e negative Fho promoters are those that are considered to be

+3 +2

negative promoter species contain Fo, Hg ions, Some suitable negative photopromotors are specially designed solutions of Metallealaen with iron (III) oxalate, iron (III) -ci.rai, Cisenflll) · .artrat, ^ uecksilber (II) -oxalai., ^ uecksilberilD-citrate and Mercury (II) - iartrate.

A related photopromoter solution is used in accordance with the present invention

by Irish of the selected Pho opromoiere with an appropriate organic solvents. i £ üi suitable organic

Solution: el can (1) mixed with the mentioned photopromoter

without its sensitivity to light being destroyed

(2) a low surface energy of typically white 25-46 dynes / cm and is (3) with the selected subscrat, e.g. B, a polyimide Compatible and wets its surface, some suitable organic

Solvents contain acetone, phenol (which on a tempera.ur

is kept above 43 C), Rleijläthylketon, acetic acid, Te ra hydrofuran, dimethylformamide and mixtures of the above

409809/1086

Solvent, where a component 1Ü - Θ0 vol. /., C. B. 10 - Θ0 vol.% Ac e on, the rest of the acetic acid, can be taken.

The selected Pho opromoter is added to the appropriate organic solvent in an amount that a concentration between a minimum of O ₁ 1 weight-7 ·, sufficient to sensitize the surface of a selected sub-surface for ultraviolet radiation, and a maximum results in percent by weight that occurs when the organic solvent or the carrier is acidic.

The area of such a consentration is again of the selected one

+2 +3

special photopromoter-Speeies, s.B. Sn, Fe and their corresponding compounds, s, B. Tin chloride, iron (III) chloride, dem desired level of light sensitivity and the specially chosen Lüsungsmittel or wetting carrier dependent. Parameters like sufficient light sensitization and related Concentrations of the photopromoter species are known to those skilled in the art and can learn from them easily and without undue experimentation be determined.

809/1086 ORIGINAL INSPECTED

The resulting wetting photo promoter solution is z. B. by immersion. Spraying or by methods that are explained in patent application P 10 17 474, 4-45, applied or formed on a surface 71 of the substrate 70. The substrate 70 with the photopromoter applied to its surface can be rinsed with water. The mentioned, applied to the surface Pho.opromoler is mil conventional Mi. a solidified layer to a 72nd A suitable mask 73, for example a quartz mask, is then applied to the photopromol layer 72. If a positive benzene photopromo.er solution is used, mask 73 is a positive mask. Areas 74 which are opaque to the radiation from which the positive mask is to be read, and with areas 76 which can transmit the desired radiation. If a negative wetting photo promoter solution is used to make a negative photo promoter layer 72, then this is the case. the mask is a negative mask, the areas 74 of which can now transmit the desired radiation and the areas 76 of which are now impermeable to it. Alternatively, using known materials, for example photoresists, and methods, areas of mass can be separated on the photopromoter layer 72

409809/1086

BATH ORIGINAL

are provided that are opaque to the radiation used.

A radiation source 77, for example for ultraviolet light of a wavelength between 1800 and 200 R, is placed over the mask 73 and set up there. If a positive wetting end

4 * 2 + S 4 * 2 photopromoter solution with e.g. Sn, Tl, Pb as Phcopromoter- Species and a positive mask 73 are used, radiation with a wavelength between 1800 and 2900 R passes through the areas 76 of the mask 73 or is transmitted through the areas mentioned and strikes the areas 72a of the Pho opromoterschicht 72. The so irradiated areas 72a of the Layer 72, which lie under the areas 76 of the positive mask 73 and correspond to them, cannot contain noble metal ions, e.g. B. Pd, made of a noble metal, ζ. B. PdCl. Contained in a solution or bath to which the irradiated substrate 70 is to be exposed, in a precious metal, e.g. B. Pd, reduce. The reason for this is that

4 * 2 4 * 3 4 * 2

the positive photopromoter species with Sn, Ti, Pb ions absorbs the radiation energy of a suitable radiation (a wavelength between 1800 and 2800 R , and the positive photo promoter resulting from the absorption of the radiation energy

409809/108 originally inspected

Species no noble metal ion In the noble metal can reduce all. The remaining areas 72b of the positive photo promoter SchidU 72, which speak to the areas 74 of the positive mask 73 and have not been exposed to any radiation can reduce the noble metal ion nooh from the noble substance, all but into the noble metal. In this way an ultraviolet radiation traces a Nes pattern or a soot of the areas 72b formed, which a Can reduce precious metal from its salt.

When a negative wetting photopromoter solution with e.g.

+2 +2

Fe and Hg and a negative mask 73 is used occurs

Radiation with a wavelength of 1800 and 2900 R wipes through the areas 74 of the mask 73 or is transferred through the areas mentioned and impinges on the areas 72b of the photopromoter layer 72. The areas irradiated in this way 72b of the layer 72, which is below the areas 74 of the negative

Mask «73 and correspond to them, no noble metal ion,

4-2 e.g. B. Pd from a noble metal salt, ι. B. PdCl ₂ , which in one

Bath is included to which the irradiated substrate 70 will be exposed is supposed to reduce into a precious metal. The explanation is that.

409809/1080 ORIGINAL INSPECTED

+3 +2

that the negative photo promoter meal with Fe - or Hg - ions when exposed to a suitable radiation (wavelength between 1800 and 2Θ00 A) whose energy is absorbed and the photopromoter species formed by the radiation absorption that Can reduce precious metal ion now into a precious metal. The remaining Areas 72a of the negative photo promoter layer 72 corresponding to the Corresponding to area 76 of the negative mask 73 and not being irradiated, no noble metal ion from the noble metal saw can pass over reduce the precious metal. In this way, a pattern or outline traced by ultraviolet radiation is made Areas formed that reduce a precious metal from its salt can.

The surface 71 of the substrate 70 and the layer T2 thereon are sufficiently exposed to ultraviolet radiation exposed until the areas 72a of a positive photopromoter layer 72 can no longer reduce an activating metal ion, or until areas 72b of a negative photopromoter layer can reduce an activating metal ion. What duration of exposure sufficient, experts easily know experimentally for a special

409809/1080 ORiGiNAL INSPECTED

Detect ultraviolet radiation. The, irradiation duration is the intensity of the radiation emanating from the source 77 dependent, i.e. on the amount of energy from the source 77 onto the surface 71 of the substrate 70 and the one located on it Layer 72 is sent out. This dependency is known or easily ascertained by those skilled in the art. The surface of the Substrate 70 and layer 72 supplied from source 77 According to the information in patent application P ID 17 474. 4-45, the amount of energy is not critical. JÜin preferred energy level

2 is between 26 and 250 lUilliwatt-seconds / cm.

The irradiated Subs rat 70 is, as already mentioned earlier and is described in the patent application P 19 17 474.4-45, In a solution that contains a noble metal ion, e. B. an ion of the metals Pd ₁ Ir, Os, R, Th, Ru, Au and Ag, some also., In which the noble metal ion is reduced to the noble metal and deposited on the areas or parts 72b of the surface 71 of the substrate 70 will. 3s it should be noted that the *. B. deposited in a pattern in the areas 72b on the substrate 70 · Noble metal layer cannot always be seen by the naked eye, but with the help of electronic instruments such as "twm an electronic"

409809/1086

microscope, an electron microscope, etc., definitely visible will.

The noble metal deposit on the substrate 70 is then placed in a conventional electroless metal plating bath, see B. Copper plating bath, immersed in which an electroless metal deposit 78, shown in FIG. 2, is deposited on the Substrate 70 is formed. Further material can then be applied or applied to the metal deposit 78, which is shown in a currentless manner be electroplated in a conventional electrolytic plating bath.

It should be noted here once again that the various Electroless deposit and electroplating solutions, plating conditions and methods are known and will not be dealt with further here. It turns back to Metallic Coating of Plastics "which covers some typical examples of both electroless and electroplating bidder and plating parameters.

It should also be noted that the present invention

in a manner similar to that in patent application P 19 17 «74.4-46

4 0 9 8 0 9/1086 ORlGlNAl, SNSPECTCD

la, can be used to produce electrical circuit patterns on a non-conductive substrate. According to FIG. 1, the areas 72b of the photopromoter see 72 form part of a pattern which is in accordance with a desired electrical smell pattern . According to FIG. 2 of the metal deposit electroless plate 78 forms part of the electrical switch, unge pattern. The resulting partially and reproduced by the metal precipitate 78 electrical Schal.ungsmuster can su to a desired thickness and electroplated dae desired Schaltungsmueter are then dissolved from the substrate by suitable means 70th

Example I.

A postive Pho opromoer solution wurd "by dissolving 1 gram SnCl .. prepared in 1 ml acetone 2H.0 Ζ \ ά commercially · available, haftflhlg coated polyester substrate was then immersed in this solution, again taken from her, and thus to a "positive photopromoter- •" not formed on the polyester substrate. The mi; The photopromote coated substrate was then washed with water and air dried.

40 * 809/1086

ORIGINAL INSPECTED

The dried substrate was then selectively irradiated for 60-90 seconds (K * 1, 800 to 2. GOO R, 100 milliwaλ-seconds / cm). The substrate was then immersed in a 0. X weight-70 aqueous PdCl solution to obtain a pattern of deposited metallic palladium. The substrate with palladium precipitate was then immersed in an electroless copper plating bath containing copper sulfate, formaldehyde, a complexing agent and an etchant in order to deposit a copper mud with good adhesion.

Example II

0.5 grams of SnCl, 2H ₂ O su 60 milliliters of phenol, which were kept at 60 ° C., were sugesetst to obtain a photopromoter solution. A polyimide substrate was immersed in the photopromoter for 1 minute, then removed therefrom and allowed to cool to room temperature. Since · substrate was then rinsed with warm water (35-40 ⁰ C), dried and then 60-seconds long ultraviolet irradiated (λ ■ 1.8βΟ - 2,900 R, 100 Miltiwatteekunden / cm). Then there was irradiation

4 0 9 8 0 9/1 0 β 6 ORiGiNAL INSPECTED

28
Subs rai in an aqueous PdCl solution of 0.1% by weight per year

dl

submerged to knock down a palladium ucall muswer. The oubs.rai. mi. the palladium-i «. egg precipitation "eventually became immersed in the electroless copper bath of Example I to obtain a patterned copper deposit.

Example III

It became 1 gram of SnCl. 2HO in one milliliter Methyläuhvlkeuon

4λ Ct

resolved. The resulting solution wetted a polyimide surface and acted as a positive photo promoter.

Example IV

It became 1 gram of SnCl ₀ . 2H.0 in one milliliter of tetrahydrofuran

Λέ A

dissolved. The resulting solution wetted a polyimide surface and act as a positive bho opromoter.

Example V

It became 1 gram of SnCl ₃ . 2HO dissolved in one milliliter of acetone. The calibration resulting solution wetted a polyimide surface

A09809 / 1 086

29 and acted as a positive Pho opromo.er.

Example VI

1 gram of SnCl .2HO was dissolved in one milliliter of glacial vinegar. The resulting solution wets a polyimide surface and serves as a positive promoter.

Example VII

It became 1 gram of SnCl. 2HO in one milliliter of a mixture of 10 vol. % Methyläthylkeion and 90 vol.% Tetrahydrofuran produced. The resulting solution wetted a polyimide surface and served as a positive photopromoter.

Example VIH

One gram of SnCl .. 2H ₂ O was dissolved in one milliliter of a mixture of 50 % by volume of methyl ethyl ketone and 50% by volume of tetrahydrofuran. The resulting solution wetted a polyimide surface and used as a positive photopromoter

409809/1086

2 3 3 9 R Π

Example IX

Ea became one gram of SnCl. 2HO dissolved in one milliliter of a mixture of 90 % by volume methyl ethyl ketone and 10% by volume tetrahydrofuran. The resulting solution wetted a polyimide surface and served as a positive photopromoter.

Example X

The procedure of Example VII was repeated except that tetrahydrofuran was replaced by acetone . The resulting solution acted as a wetting positive photopromoter.

Example XI

The procedure according to Example VHI was repeated, except that tetrahydrofuran was replaced by acetone. The resulting solution acted as a wetting positive photopromoter.

Example ΧΠ The procedure of Example IX was repeated except that

409809/1086 original inspected

Tetrahydrofuran was replaced by acetone. A wetting positive photopromoter was shown.

Example XIU

The procedure of Example VH was repeated except that Tetrahydrofuran was replaced by acetic acid. It became a benetsender positive photopromoter shown.

Example XIV

The procedure of Example VIII was repeated except that Tetrahydrofuran was replaced by acetic acid. A wetting positive photopromoter was shown.

Example XV

The procedure of Example DC was repeated except that tetrahydrofuran was replaced with acetic acid. It was a wetting positive photo promoter shown.

409809/1086

Example XV I

It became one gram of SnCl. 2HO dissolved in one milliliter of a mixture of 10% by volume of tetrahydrofuran and 90 % by volume of acetone. The resulting solution acted as a wetting positive photopromoter.

Example XVH

Ee became one gram of SnCl. 2HO in one milliliter of a mixture Dissolved from 50% by volume of tetrahydrofuran and 60% by volume of acetone. The resulting solution acted as a wetting positive photopromoter.

Example XVIII It became one gram of SnCl. 2H.0 in one milliliter of a mixture

ti ά

of Θ0% by volume of tetrahydrofuran and 10% by volume of acetone dissolved · The the resulting solution acted as a wetting positive photo promoter,

Example XIX The procedure of Example XVI was repeated except that

409809/1086

Acetone was replaced by acetic acid. The resulting solution wetted a polyimide surface and acted as more positive Photopromoter.

Example XX

The procedure of Example XVII was repeated except that acetic acid was substituted for acetone. The resulting Solution formed a wetting positive photopromoter.

Example XXI

The procedure of Example XVUI was repeated except that Ac eton was replaced by acetic acid. The resulting solution formed a wetting positive photopromoter.

Example ΧΧΠ It became one gram of SnCl-. 2H.0 in a milliliter one

i Λ

Dissolved mixture of 10% by volume acetone and 90% by volume acetic acid. The resulting solution wetted a polyimide surface and acted as a wetting positive photopromoter.

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example ZSiJJl

It became one gram of SnCl. 2HO dissolved in one milliliter of a mixture of 50 Vol. Io acetone and 50 Vol. It acetic acid. The resulting solution wetted a polyimide surface and acted as a positive photo promoter.

Example XXIV

It became one gram of SnCl. 2HO dissolved in one milliliter of a mixture of Θ0 vol. Jo acetone and 10 vol.% Acetic acid. The resulting solution acted as a wetting positive photopromoter.

example XXV

The procedure of Example vn was repeated except that one gram of mercury earth chloride was dissolved in one milliliter of the mixture. The resulting solution wetted a polyimide * surface and acted as a negative photopromoter.

example XXVI

The procedure of Example VIII was repeated except that

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one gram (^ ueckeilberdD-chloride in one milliliter of the mixture was dissolved. The resulting solution wetted a polyimide surface and acted as a negative photopromoter.

Example XXVlI

The procedure of Example IX was repeated except that one gram of mercury to O-chlorine in one milliliter of the mixture was dissolved. The resulting solution acted as a wetting negative photopromoter.

Example XXVUI

The procedure of Example 10 was repeated except that 1 gram of mercury DO fluid in one milliliter of the mixture was dissolved. The resulting solution acted as a wetting negative photopromoter.

Example XXIX The procedure of Example XI was repeated except that

1 gram of mercury (II) chloride in one milliliter of the mixture

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was dissolved. The calibrating solution was more wetting negative photopromoter.

Example XXX

The procedure of Example XII was repeated except that one gram of mercury (II) chloride was in one milliliter of the solution was dissolved. The calibrated solution acted as a Benet Bender negative photo promoter.

Belgpiel XXXI

The procedure of Example ΧΠΙ was repeated except that one gram of mercury (II) chloride in one milliliter of the mixture was dissolved. The calibrated solder acted as a wetting negative photopromoter.

example XXXIf, The procedure of Example XIV was repeated except that

one gram of mercury (II) chloro! in one milliliter of the mixture was dissolved. The resulting solution acted as a

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wetting negative photopromoter.

Example XXXIII

The procedure of Example XV was repeated except that one gram of QuecusilverdIJ chloride was dissolved in one milliliter of the mixture . The resulting solution acted as a wetting negative photopromoter.

Example XXXIV

The procedure of Example XM was repeated except that one gram of mercury (Π) chloride was dissolved in one milliliter of the mixture. The resulting solution acted as a beneating negative photopromoter.

Example XXXV

The procedure of Example XVII was repeated except that one gram of mercury over UD chloride was dissolved in one milliliter of the mixture. The resulting solution acted as a beneating negative photopromoter.

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Example XXXVI

The procedure of Example XVIII was repeated except that one gram of Queek Silver (II) chloride was dissolved in one milliliter of the mixture. The resulting solution acted as a wetting negative photopromoter,

Example XXXVII

The procedure of Example XDC was repeated except that one gram of mercury chloride was dissolved in one milliliter of the mixture . The resulting solution acted as a wetting negative photopromoter

example XXXVni

The procedure of Example XX was repeated except that one gram of Queeks Over (II) chloride was dissolved in one milliliter of the dtr mixture. The resulting solution acted as a wetting negative photopromoter

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30th

Pci game XXXIX

The procedure of Example XXI was repeated except that one gram of mercury over (II) chloride in one milliliter of the mixture was dissolved. The resulting solution acted as a wetting negative photopromoter.

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Claims (5)

ν. iJSrjJKK üL.iirTltir COMPANY Lando 4 Incorporated NEV. YORK. N. Y. 10007 United States P A Γ JC N Γ A N S P It Ü ΓΗ Ε fly method of depositing a metal on a surface a non-conductive substrate through which at least a portion of the substrate surface for electroless metal deposition rendered receptive and in which this portion of the substrate surface is immersed in an electroless metal plating solution is immersed in order to deposit metal on it electrolessly, with the absorption capacity by one of the following Step causes: (a) Senslilation of the part of the surface with a Sensitizer of a sensitizing species and activating the sensitized surface or (b) Coating the surface with a photopromoter * 4 "2 + ^? · 4 · 2 * f" *? +9 Solution of one of the Sn -, Ti - Pb - «fe and Hg - 409809/1086 ion group selected apezies selekiives> irradiation of the coated surface with ultraviolet.er radiation to delimit the part that can reduce a precious metal from a precious metal salt solution and immersing the delimited part in a precious metal salt solution to form a precious metal deposit on it, characterized in that either the The sensitizer or the photopromoter solution is mixed with a suitable organic solvent selected from the group of acetones, phenols, cracked acids, methylethylkeions, tetrahydrofurans, dimethylformamides and mixtures thereof. 2. The method according to claim 1, characterized in that the b Bnsibüisatorspezies (a) at least one Sn ⁺² -. Contains Ti ⁺³ , Pb ⁺² and Hg ⁺¹ ions. 3. The method of claim 1 or 2, characterized in that the activation of the surface seneibilisierten includes reducing a selected from Ir, Oe, Pd, Pt, Kh ₁ lid, Au and Ag katalytiechen metal from a Metallaalslösung by the eeneibiliaierende Spexies. 409809/1086 2339B07 4. The method according to claim 1, characterized in that the noble metal consists of Ir, Oe, Pd, Pt, Ich, iai. Au and Ag is selected. 5. Metal deposit, characterized by its production according to the method according to one of the preceding claims. 4Q9809 / 1Q86