WO1997019204A1 - Method and apparatus for surface treatment - Google Patents

Abstract

A method and apparatus for surface treatment, wherein a workpiece is exposed to an activated gas containing nitrogen and water at an atmospheric pressure to modify the surface of the workpiece. To improve wettability of a soldered lead frame (12), oxygen is fed from a gas supply (619) to a plasma generator in a surface treatment unit (30) through a first pipe (657). Nitrogen is fed from the gas supply (619) into a container (659) of pure water (660) through a second pipe (658), and the wet nitrogen is introduced to the plasma generator in the surface treatment unit (30). The gas supplied into the plasma generator is excited and decomposed by an electrode to which a D.C. voltage or a low-frequency A.C. voltage of not higher than 50 KHz is applied, and a plasma containing nitrogen oxides is generated. An IC (10) is exposed to this plasma for the surface treatment of the lead frame (12). Oxides on the surface of the lead frame (12) are reduced or their oxides are substituted by nitrogen oxides, and the surface of the lead frame (12) is modified.

Description

 Description Surface treatment method and apparatus

 [Technical field]

 The present invention relates to a surface treatment method for modifying a surface of an object to be processed, such as a semiconductor device, a crystal oscillator, a circuit board, or a wire, and a surface treatment method and an apparatus therefor.

 [Background technology]

Conventionally, a method of cleaning a metal surface with hydrogen atoms generated by vacuum plasma (Japanese Patent Laid-Open No. 2-190489) and a method of improving solder wettability of a substrate by vacuum plasma cleaning (Japanese Unexamined Patent Publication No. 3-174792) has been proposed. The present applicant has already proposed a technology for activating gas by atmospheric pressure plasma instead of the conventional vacuum plasma, and improving the wettability of a work to be soldered by active species such as ions and excited species. (W094 / 222628, Japanese Patent Application No. 7-29550) ₍ Here, in the above-described processing using vacuum plasma and atmospheric pressure plasma, both are excited by plasma. Metakinesis is performed with the active species.

 Here, the direct discharge treatment method in which the object to be processed is exposed to plasma is not preferable because the physical properties of the object to be processed are likely to be destroyed due to plasma damage. In particular, if the surface of the object to be processed is a metal, strong plasma is generated intensively at the protruding portion, and the entire surface to be processed cannot be uniformly processed.

 On the other hand, there has been proposed an indirect discharge treatment method in which an active electrode generated in a plasma generation unit is guided to an object disposed at a position not exposed to plasma for treatment. In this case, the above-described plasma damage does not occur.

 However, since this active species has a long life and its life is relatively short, placing the workpiece far from the plasma generation unit makes it impossible to perform the surface treatment or increases the processing efficiency. It will drop significantly. Therefore, this indirect discharge treatment method is not practical because there are restrictions on the installation location of the object to be treated.

In addition, for example, there is a method of performing surface treatment using fluorine F2 obtained by discharge-decomposing CF4.However, when recovering fluorine as a corrosive gas without releasing it to the atmosphere, it includes aluminum oxide. Using a trap device. This trap device By trapping the element with aluminum oxide, aluminum fluoride is generated. Since this aluminum fluoride can only be disposed of by a specialized contractor, there is also a problem that exhaust processing takes time and costs.

 Therefore, an object of the present invention is to provide a surface treatment method and a device capable of performing a treatment for modifying the surface of an object to be processed in a state where there is no plasma damage, and having a high degree of freedom in an installation place of the object. Is to do.

 Still another object of the present invention is to provide a surface treatment apparatus capable of performing surface treatment for modifying the surface of an object to be treated with low running cost from gas or liquid which can be obtained at low cost, and a method thereof.

 It is still another object of the present invention to provide a surface treatment method and a device capable of modifying the surface of a target object while suppressing generation of ozone that oxidizes the target object. .

 It is still another object of the present invention to provide a surface treatment method and an apparatus therefor, in which the treatment after trapping the exhausted treatment gas is easy and the running cost can be reduced.

 [Disclosure of the Invention]

 The present invention is characterized in that the surface of the object to be treated is treated by bringing a treatment gas containing nitrogen oxide into contact with the surface of the object to be treated.

 These nitrogen oxides can reduce the oxides formed on the surface of the object to be reformed and modify the surface of the object. Alternatively, the nitrogen oxide may replace the oxide formed on the surface of the object with nitrogen oxide combined with a substance forming the surface to modify the surface of the object. it can.

As the process gas containing the nitrogen _{oxides, N 2 0, N 0,} N 0 2 as possible out and the like.

The case where the surface of the object to be processed is preliminarily soldered and the surface that has been oxidized after the soldering is modified by the above processing gas will be described as an example. In this case, lead oxide PbO or tin oxide SnO is formed on the surface of the object. The nitrogen oxides react with these oxides as described below to modify the surface of the object. For example, if N ₂ is used as the processing gas, 2 Pb 0+ 2 N〇 ₂ → P b (N〇 ₃ ) 2 + P b '(1), and the oxide PbO on the surface of the workpiece is replaced with nitrogen oxide Pb (N0 ₃ ) ₂ You.

Also, when N ₂と し て is used as the processing gas,

_{PbO + N 2 0- 2NO + Pb} ... (2) , and this case, the Pb is reduced oxide PbO of the surface of the object. At this time, NO is generated, which further contributes to the modification of the surface of the object to be processed.

 If NO is used as the processing gas,

P bO + NO → N_〇 ₂ + Pb - (3), and the oxide PbO in this case the surface of the object is being reduced Pb. At this time, N0 ₂ is generated, which further contributes to the modification of the street above the surface of the object. Here, when the oxide PbO is reduced to Pb, for example, the wettability of the solder is improved. Also by replacing the oxide PbO nitrogen oxides Pb (N0 _{3) 2,} but not to the extent situ Go the reduction is improved wettability of the solder. Substitution with nitrogen oxide Pb (NOs) ₂ is excellent in that it is not oxidized even after being left in the air for a relatively long time after the surface treatment of the present invention. The above is similarly applied to other oxides such as the oxide S ηθ.

As described above, it can be seen that in the present invention, the surface of the object to be processed can be modified by using nitrogen oxides such as N ₂₀ , N 0, and NO 2 as the processing gas.

Another process gas containing the nitrogen oxides, mention may be made of a gas containing HN0 _3, HN_〇 _2, H ₂ N ₂ 0 ₂ acid and the like.

With the gas containing HN0 ₃ as the processing gas,

_{PbO + 2HN0 3 → Pb (N0} 3) 2 + H2O "'(4) , and the Ru is an oxide PbO of the surface of the object is a substituted nitrogen oxides Pb (NOs) _2.

Moreover, the use of gas containing HN0 ₂ as a process gas,

_{PbO + HN0 2 → Pb + HN0} 3 ... (5) , and this case is also oxide P b 0 of the object surface nitrogen oxides P b (NO ₃₎ is replaced by 2. At this time, HN0 ₃ occurs, which further contributes to the modification of the object I do.

As the process gas, the use of gas containing H ₂ N ₂ 0 _2,

2 Pb 0 + H ₂ N ₂ 〇 ₂ → 2 Pb + 2 HN 0 _2- (6) In this case as well, the oxide Pb〇 on the surface of the object to be treated is reduced to Pb. At this time, HN0 ₂ occurs, which further contributes to the modification of the object.

In the present invention, the above-described processing gas may be supplied directly from the cylinder to the object to be processed, or the processing gas may be generated and supplied by any of the following methods. As one method of generating the processing gas, the processing gas can be generated by generating a discharge in an atmosphere in which a supply gas containing oxygen atoms (0) and nitrogen atoms (N) is supplied. . The feed gas can Rukoto like for example an oxygen gas 0 ₂ and nitrogen gas N _2. Other feed gases, to oxygen gas 0 ₂ and nitrogen gas N ₂ can be mentioned those of pure water was added to the water H ₂ 0 Japanese. Further, other supply gases include, but are not limited to, nitrogen gas N ₂ and water H ₂₀ , or compressed air and water H ₂₀ .

These feed gas is decomposed by electric discharge, by binding an oxygen atom (0) and nitrogen atom _{(N), N 2 0,} N0, N0 2 is generated. Therefore, a reaction of one or more of the above-described formulas (1) to (3) occurs, and the surface of the object to be processed can be modified.

Further, the hydrogen atom by the addition of water H ₂ 0 (H) is present, by reaction as described below, HN0 _3, HN_〇 _2, H ₂ N ₂ 0 ₂ may also be generated.

_{2NO + 4H 2 0 → 2HN0 3} + 3H 2 ··· (7)

_{2NO + 2H 2 0 → 2HN02 +} H 2 - (8)

2 ΝΟ + 2 H ₂ 0 → H ₂ N ₂ 〇 ₂ + H ₂ + 0 _2- (9) Therefore, by the addition of water, one or more of the reactions (1) to (3) and (4) It can be seen that any one or more of the reactions (6) to (6) are performed to modify the surface of the object to be processed. For this reason, there is an advantage that the efficiency of the modification treatment of the surface of the object to be treated is increased. The reaction of equation (7) is less likely to occur than equations (8) and (9). Therefore, HN0 ₃ is hard to be generated, Itanyu0 _2, since ΗζΝ ₂ 0 ₂ is relatively large product, by reaction of the above equation (5) (6), since the oxide is reduced, the target object The efficiency of the surface reforming process is further improved. A pair of electrodes to which a low frequency AC or DC voltage of 50 kHz or less is applied at or near atmospheric pressure to generate a discharge that excites the supply gas can be used.

 When the low-frequency AC voltage or DC voltage described above is applied between a pair of electrodes, the peak-to-peak voltage of the discharge voltage can be relatively increased, and the discharge voltage can be stabilized without supplying He or the like which is a plasma generation gas. To generate a discharge. It is not necessary to use He to generate such a stable atmospheric pressure plasma, and the running cost can be reduced.

As another method for generating the processing gas, the processing gas can be generated by heating an atmosphere in which a supply gas containing oxygen atoms (0) and nitrogen atoms (N) is supplied. As the supply gas, the same gas as in the case of discharge decomposition can be adopted. The feed gas is decomposed by thermal _{energy, N 2 0, N0, NO} 2 is produced. In this case also, the hydrogen atom (H) is present, HN 0 ₃ Many _{HN0 2, H 2 N 2 0} 2 made fresh from increases the processing efficiency.

 Here, the pair of electrodes for plasma generation has first and second electrodes arranged with a dielectric interposed therebetween, and the first and second electrodes are connected to each other on each surface facing the dielectric. It is preferable that first and second recesses are formed at non-directional positions, and a supply gas is introduced into at least one of the first and second recesses.

 This reduces the stray capacitance between the first and second electrodes. Since the power consumed by the stray capacitance can be used as the discharge power, stable plasma can be maintained or the plasma density can be increased, and the processing rate can be improved.

Still another method of generating the processing gas includes irradiating an atmosphere supplied with a supply gas containing oxygen atoms (0) and nitrogen atoms (N) with light to generate the processing gas. it can. The feed gas of this case be the same as the above case, the feed gas is _{photolyzed, N 2 0, N0, N0} 2 is generated. Again, the hydrogen atom (H) is present, HN 0 ₃ more than _{HN0 2, H 2 N 2 0} 2 is produced, the process efficiency is increased.

In any of the above three methods, oxygen (O ₂ ) gas and nitrogen It is preferable to use elemental (N ₂ ) gas and to also use nitrogen gas as a carrier gas. Since nitrogen gas is inexpensive, the running cost can be reduced even when used in large quantities as a carrier gas.

As a method to include water H ₂ 0 in the feed gas, at least one feed gas, may be contacted at the middle supply of that water. When water is contained in the supply gas, the humidity of the processing gas generation atmosphere increases, and there is an advantage that generation of ozone that oxidizes the object to be processed can be suppressed.

 Here, by changing the setting of the flow ratio between the oxygen gas and the nitrogen gas, the type of the processing gas to be generated can be changed. According to experiments performed by the present inventors, it was confirmed that N 2 O could be generated when the supply amount of oxygen gas was 15% by volume or less. N 2 O as a processing gas contributes to the modification of the surface of the object to be processed, for example, as in the above-mentioned formula (3).

Further, according to experiments of the present inventors, when the supply amount of the oxygen gas exceeds 1 0 vol%, that N 0 ₂ is produced as a processing gas was confirmed. N 0 ₂ as a processing gas, as the above equation (1), and an oxide of the surface of the object is replaced with nitrogen oxides, it is possible to modify the surface of the object. In this case, for example, since in improving solder wettability poorer effect than in the case of reduction, in order to reduce the generation of N 0 _2, the supply use of oxygen to 1 0% by volume or less I just need.

Further, according to experiments in the present invention and the like, it was confirmed that when the supply amount of oxygen gas was 3% by volume or less, N ₂₀ was generated as a processing gas. N ₂ 0 as the processing gas can modify the surface of the object to be processed, as in the above formula (2). However, the absolute amount of oxygen supply amount is supplied that it more than 3% of the oxygen gas is small, because even small amounts of N ₂ 0 that occur, the processing rate is lowered.

In consideration of the above, the supply amount of oxygen is preferably 15% by volume or less, and more preferably 10% by volume or less. More preferably, the content is set to 5 to 10% by volume, and it has been found that the efficiency of reforming the surface of the object to be treated is superior to the case where the oxygen supply amount is outside this range. The optimal value of the supply amount of oxygen is around 10% by volume at which the generation amount of NO ₂ is maximized.

Yet another method of generating process gas is to use a salt composed of metal and nitrogen compounds. W

 7

Is to electrolyze the aqueous solution to produce nitrogen compounds. Ri by this electrolysis, can generate _{HN0 3, HN0 2, H 2} N 2 0 2.

Yet another method for generating a treatment gas, is to contact the Kiyariagasu to any aqueous solution of Kano acid _{H 2 N 2 0 2, HN} 02, HN0 3. When the carrier gas contains the above-mentioned acid, the surface of the object to be processed can be modified by, for example, any one of the above-described formulas (4) to (6).

 In the present invention, it is preferable that the method further includes a step of forcibly exhausting the processing gas and the reaction product supplied to the object to be processed, and a step of trapping the processing gas and the reaction product in the middle of the exhaustion. . For this purpose, the device of the present invention includes a forced exhaust means and a trap means. As a result, it can be recovered without scattering it to the atmosphere such as nitrogen oxides. In particular, catalysts for recovering nitrides and the like, and purifying means for activated carbon and the like can be easily discarded and can reduce running costs.

 An object to be processed suitable for this type of processing includes a circuit board, an electronic component such as an integrated circuit (IC), a wire to be soldered, or a crystal unit.

 [Brief description of drawings]

 FIG. 1 is a schematic explanatory view showing an embodiment of the present invention in which a processing gas is generated by a discharge decomposition method.

 FIG. 2 is a schematic explanatory view showing an embodiment of the present invention in which a processing gas is generated by a pyrolysis method.

 FIG. 3 is a schematic explanatory view showing an embodiment of the present invention in which a processing gas is generated by a photolysis method.

 FIG. 4 is a schematic explanatory view showing an embodiment of the present invention for generating a processing gas by an electrolysis method.

 FIG. 5 is a schematic explanatory view showing an embodiment of the present invention in which an aqueous solution of an acid is brought into contact with a carrier gas to generate a processing gas.

 FIG. 6 is a schematic explanatory view showing an embodiment of the present invention in which a supply gas is brought into contact with water to generate a processing gas.

FIG. 7 is a characteristic diagram showing the wettability of solder of a work surface-treated according to the embodiment of the present invention. FIG. 8 is a schematic diagram illustrating measurement of the wettability of the solder in FIG. FIG. 9 is a schematic explanatory view showing the entire configuration of the surface treatment apparatus according to the embodiment of the present invention.

 FIG. 10 is a schematic explanatory view showing the internal configuration of the surface treatment unit shown in FIG.

 FIG. 11 is a schematic explanatory view showing the configuration of the plasma generating section shown in FIG. FIG. 12 is a schematic explanatory view showing another first embodiment of the processing gas generator shown in FIG.

 FIG. 13 is a schematic explanatory view showing another second embodiment of the processing gas generator shown in FIG.

 FIG. 14 is a schematic explanatory diagram showing another first configuration of the plasma generating unit. FIG. 15 is a schematic explanatory view showing another second configuration of the plasma generating unit. FIG. 16 is a schematic explanatory view showing another first internal configuration of the surface treatment unit shown in FIG.

 FIG. 17 is a schematic explanatory view showing another second internal configuration of the surface treatment unit shown in FIG.

 FIG. 18 is a schematic explanatory view showing an embodiment in which a line type processing apparatus is constituted by a surface treatment unit.

 FIG. 19 is a schematic sectional view showing the air supply / exhaust section of the surface treatment unit shown in FIG.

 FIG. 20 is a schematic explanatory view showing an embodiment in which a processing apparatus for a stand and a eve is constituted by a surface treatment unit.

 FIG. 21 is a schematic sectional view showing a supply / exhaust section of the surface treatment unit shown in FIG.

 FIG. 22 is a schematic explanatory view showing an embodiment in which a rod-type processing apparatus is constituted by a surface treatment unit.

 FIG. 23 is a schematic sectional view showing a supply / exhaust portion of the surface treatment unit shown in FIG.

Fig. 24 shows the construction of a toaster-type processing unit using a surface treatment unit. It is a schematic explanatory view showing an example.

 FIG. 25 is a schematic sectional view showing a supply / exhaust section of the surface treatment unit shown in FIG.

 FIG. 26 is a schematic explanatory view showing an embodiment in which a batch processing type processing apparatus is constituted by a surface processing unit.

[Best Mode for Carrying Out the Invention]

 Hereinafter, the surface treatment method and the surface treatment apparatus of the present invention will be specifically described with reference to the drawings.

 How to generate process gas>

In the present invention, a processing gas containing nitrogen oxides N ₂₀ , N 0, NO H ₂ N ₂ O ₂ , HN 02, HNOs, etc. is brought into contact with the processing object, and the surface of the processing object is modified by this highly reactive processing gas. The quality is being processed. This highly reactive processing gas may be supplied from the cylinder to the workpiece via the supply pipe, but the processing gas is generated by any of the six methods shown in Figs. 1 to 6. You can also.

 1 to 6, a common configuration includes a processing gas generation container 1 and a processing gas supply pipe 2 that guides the generated processing gas toward an object to be processed.

 (Discharge decomposition method)

 In the embodiment shown in FIG. 1, oxygen atoms (0) and nitrogen atoms (N), which are processing gases, are treated in a processing gas generation vessel 1 to which a processing gas supply pipe 2 and a supply gas supply pipe 3 are connected. The supplied gas is decomposed by the discharge at or near atmospheric pressure to generate the processing gas. For this purpose, a plasma generating section 4 having a pair of electrodes is provided in the processing gas generating container 1.

Using the apparatus of FIG. 1, nitrogen gas N ₂ was supplied at 5 liters / min as a supply gas.Oxygen gas was supplied at 200 cc / min each, and-the power supply frequency supplied to the pair of electrodes was changed. At about 10 kHz, a discharge was generated at a peak-to-peak discharge voltage of AC 10 kVpp. At this time, in this example, the supply amount of oxygen was approximately 3.85% by volume (100 × 200/5200), and oxygen and nitrogen were decomposed to generate NO. By supplying this NO to the object as a processing gas, As shown in the above equation (2), the surface of the object to be processed could be modified.

Incidentally, as described above, by changing the supply amount of oxygen, it is possible to increase the generation amount NO, the or a other nitrogen oxides N ₂ 0, N0 _2, etc. can also be generated.

 In addition, as described above, the use of a power supply frequency as low as 10 kHz enabled stable discharge without supplying He. As a result, the running cost can be reduced. In order to stably generate a discharge without supplying He, the peak-to-peak voltage of the discharge voltage must be higher than a certain value using a low frequency. According to the experiments of the present inventors, the above-described discharge can be confirmed at each of the AC voltages of DC voltage, 10 kHz, 30 kHz, and 40 kHz, and from the viewpoint of securing a large peak-to-peak voltage of the discharge voltage, 50 kHz An AC or DC voltage with a low frequency below z has been found to be useful.

 (Pyrolysis method)

In Figure 2, instead of the heater 4 of FIG. 1, the feed gas such as oxygen gas 0 ₂ and nitrogen gas N ₂ is provided with a heater 5 for heating the process gas generation container 1 to be introduced . Then, in the second figure, in the process gas generating vessel 1 and the feed gas is thermally decomposed by thermal energy, that is generating a process gas containing nitrogen oxides N ₂ 0, N0, N0 _2.

In this embodiment, the same kind of gas as the embodiment of FIG. 1 was supplied at the same flow ratio as the supply gas. When the set temperature of the heater 5 was set to 800 ° C., NO was able to be generated as a processing gas, as in the embodiment of FIG. In this case also, by changing the supply amount of oxygen, it is possible to increase the generation amount NO, the or N ₂ 0 is another nitrogen oxide, N0 _2, etc. can also be generated.

 (Photolysis method)

 In the embodiment shown in FIG. 3, in the processing gas generation vessel 1 to which the processing gas supply pipe 2 and the source gas supply pipe 3 are connected, the supply gases, for example, oxygen gas and nitrogen gas are photo-decomposed. To generate process gas. For this purpose, a UV lamp 6 for irradiating light, for example, ultraviolet light, is provided in the processing gas generation container 1.

Oxygen and nitrogen gas were supplied as the supply gas at the same flow ratio as in the embodiment of Figs. When the lamp output of the UV lamp 6 is set to 100 mW / cm ² and the wavelength of the emitted light is set to 400 nm, NO is generated as a processing gas as in the embodiment of FIGS. 1 and 2. I was able to. Also in this case, by changing the supply amount of oxygen, the generation amount of N 0 can be increased, or other nitrogen oxides such as N ₂₀ and NO 2 can be generated.

 (Electrolysis method)

In the embodiment of FIG. 4, a processing gas is generated by electrolyzing an aqueous solution of a salt composed of an alkali metal and a nitrogen compound in a processing gas generation vessel 1 to which a processing gas supply pipe 2 is connected. . For this purpose, an aqueous solution of the above-mentioned salt aqueous solution was accommodated in the processing gas generation container 1, and the electrodes 8 a and 8 b were arranged in each area partitioned by the partition plate 7. The electrodes 8 a, 8 b in the example was applied to DC 24 V, and can generate a processing gas containing _{HN0 3, HN0 2, H 2} N 202.

As the aqueous solution of a salt suitable for electrolysis, can be cited NaN0 _3, KN0 ₃ nitrate such as, nitrite, such as N a N0 _2, an aqueous solution of the following nitrite such as N a NO.

(Regarding the contact method between the aqueous acid solution and the carrier gas) In the embodiment shown in FIG. 5, the processing gas supply pipe 2 also serving as a carrier gas supply pipe is a first branch pipe that guides the carrier gas into the processing gas generation vessel 1. 2a, and a second branch pipe 2b for leading out the processing gas generated in the processing gas generating container 1. The carrier gas HN0 _3, HN0 ₂ or is contacted with an aqueous solution of H ₂ N ₂ 0 ₂ acid to generate a processing gas containing a liquid of the acid. By bringing the carrier gas containing the acid liquid into contact with the object to be processed, the surface of the object to be processed can be modified by any of the reaction formulas (4) to (6) described above.

 (About the contact method between supply gas and water)

Here, in the embodiment shown in FIGS. 1 to 3, it is preferable to introduce water H ₂₀ into the processing vessel 1. FIG. 6 shows a modification of the embodiment of FIG. And a second gas supply pipe 3b for supplying the other gas, and a container 9 for bringing the other gas into contact with water in the middle of the second gas supply pipe 3b. Obedience Then, the other gas containing water is introduced into the processing gas producing container 1. Result of this, the reaction is mainly caused in the above-mentioned formula (8) (9), HN 0 2 or will contain H ₂ N ₂ 0 ₂ as a process gas. As a result, the reactions of the above-mentioned formulas (5) and (6) mainly occur, and the surface treatment of the object to be processed can be promoted.

 Further, when water is contained in the supply gas, the humidity in the processing gas generation container 1 increases, and as a result, generation of ozone that oxidizes the target object is suppressed.

 (Evaluation of improvement of wettability of target object) Here, the target object was used as an IC lead frame, and the wettability of the surface-treated lead frame 12 was evaluated. FIG. 7 shows the evaluation results. In FIG. 7, the evaluation value of the wettability of the lead frame is indicated by the value of the buoyancy acting on the lead frame. The value of buoyancy reflecting this wettability is, for example, a value measured by a measuring device schematically shown in FIG.

 In the measuring apparatus shown in FIG. 8, a panel 701, which is an elastic body, is connected to one end of a surface-treated lead frame 12 and the other end of the lead frame 12 is The buoyancy is measured as the tension of the lead frame 12 with respect to the panel 01 when immersed in the solder 703 and lowered. When the wettability of the solder is poor, the solder flips the lead frame 12 and the lead frame 12 moves in the direction of arrow a. At this time, the tension on the panel 701 becomes a negative value. On the other hand, when the wettability of the solder is good, the lead frame 12 moves in the direction of arrow b. At this time, the tension applied to the spring 701 is a positive value.

 Using the measuring device shown in FIG. 8, measurements were made on a plurality of lead frames 12 processed by changing the kind of supply gas. As shown in FIG. 7, when no surface treatment was applied to the lead frame 12, the solder wettability was poor and the buoyancy was a negative value.

On the other hand, when oxygen and hydrogen were used as the supply gas and the supply amount (volume%) of oxygen was changed, the buoyancy became a brass value in each case, indicating that the wettability of the solder was improved. In particular, it can be seen that the value of buoyancy was maximum when the supply amount of oxygen was 10% by volume, and that the wettability of the solder was most improved. Furthermore, when the supply amount of oxygen was 5 to 10% by volume, it was found that the wettability of the solder was improved as compared with the case of other supply amounts. Call

Furthermore, when nitrogen and oxygen (15% by volume) were supplied and water was added, the positive value of buoyancy increased compared to the case where no water was added. This, as described above, would contain HN0 ₂ or H ₂ N ₂ 0 ₂ as a process gas, solder wettability indicating that further improved.

 Also, when the supply gas was N2 + H20 and when the supply gas was compressed air + H20, the buoyancy was a positive value, indicating that the solder wettability was improved.

 Here, the processing gas generated in the processing gas generation container 1 of the present invention can maintain the high reactivity of the processing gas until the processing gas is exposed to the object. On the other hand, the active species such as fluorine radicals generated in the plasma generation unit as in the conventional art have their lifetimes interrupted during the exposure to the workpiece disposed outside the plasma generation unit. In this regard, the present inventors conducted the following experiment.

 If the processing gas supply pipe connected to the plasma generation unit is a 1 / 4-diameter size (6.35 mm in outer diameter and 3.17 mm in inner diameter) that is generally used as a piping tube, the supply gas flow rate and tube cross-sectional area From this, I tried to find the flow rate of the processing gas. If the flow rate of the supply gas is 100 cc / min, the flow rate of the processing gas is 21.12 cm / s. Since the lifetime of the fluorine radical is 1/1000 s or less, it can be seen that the fluorine radical disappears at a position 0.012 cm away from the plasma generating part.

 Example overall configuration of the apparatus>

FIG. 9 is a schematic explanatory view showing the entire configuration of the surface treatment apparatus according to the present embodiment. In the embodiment shown in FIG. 9, the work to be soldered is an IC 10, and the IC 10 is placed on, for example, a conveyor line 14, and is sequentially conveyed in a direction from the back surface to the front surface of the drawing. Here, the lead frame 12 of the IC 10 has been solder-plated in advance. Therefore, although the surface of the lead frame 12 is covered with lead Pb and tin Sn, it is oxidized to lead PbO and tin oxide SnO. The present embodiment reduces the lead oxide PbO and tin oxide SnO formed on the surface of the lead frame 12 to reduce the wettability of the solder of the lead frame 12. To improve the performance. In order to surface-treat the lead frame 12 of the IC 10, a surface treatment unit 30 and an air supply connection pipe 20 and an exhaust connection pipe 24 connected thereto are provided.

 The processing gas generated inside the surface treatment unit 30 is introduced into the air supply connection pipe 20, and is processed through the air supply section 22 which spreads on the umbrella above the IC 10. The gas is exposed to the IC 10, especially the lead frame 12. The exhaust connection pipe 24 is for sucking the processing gas exposed to the lead frame 12 and forcibly exhausting the processing gas through the surface processing unit 30.

 The supply gas from the supply gas generator 600 is supplied to the surface unit 30. The supply gas generation section 600 is provided with a gas output section 6 19, a first gas supply pipe 657, a second gas supply pipe 658, and a steam mixer 659.

 Oxygen and nitrogen, nitrogen alone, or compressed air are supplied as supply gases from the gas output section 6 19.

 A first gas supply pipe 657 and a second gas supply pipe 658 composed of two gas supply pipes 658a and 658b are connected to the gas output section 619. .

 The first gas supply pipe 657 is provided with a valve 662 for ON-OFF the supply gas output and a flowmeter 664 for adjusting the flow rate of the supply gas. The flow rate of nitrogen and oxygen, nitrogen, or compressed air from the gas output section 6 19 is adjusted by a flow meter 664 via a valve 662 of a first gas supply pipe 657.

 Of the second gas supply pipes 658, the gas supply pipe 658a is provided with a valve 636 for turning on / off the supply gas output, and the gas supply pipe 658b is supplied with the supply gas. A flow meter 666 for adjusting the gas flow is provided. The gas supplied from the gas output section 6 19 is introduced into the steam mixer 659 via the valve 663 of the gas supply pipe 658a, and is supplied to the steam mixer 659 by water, for example, pure water 6 60 is heated by the heater 661, and is turned into steam. As a result, the supply gas introduced into the steam mixer 659 contains steam. The supply gas containing this moisture is introduced into the gas supply pipe 658b, and the flow rate is adjusted by the flow meter 665.

Thus, in the first gas supply pipe 657, a supply gas containing no water is led, In the second gas supply pipe 658, a supply gas containing water is led. The ratio of the water-free gas supplied to the surface treatment unit 30 to the water supplied gas depends on the ON / OFF of the valve 652 of the first gas supply pipe 657 and The flow rate can be arbitrarily adjusted by adjusting the flow rate of the flow meter 664, turning on / off the valve of the second gas supply pipe 658, and adjusting the flow rate of the flow meter 666.

 By performing the surface treatment with the configuration shown in FIG. 9, the wettability of the lead frame 12 of the IC 10 can be improved.

 (Structure of surface treatment unit 30)

 As shown in FIG. 10, the surface treatment unit 30 includes a gas supply pipe 40, a power supply 50, a plasma generation section 60, an exhaust pipe 70, and trap means inside one housing 32. It is equipped with a catalyst 80.

 The gas supply pipe 40 is connected to the upstream and downstream sides of the plasma generation section 60 shown in FIG. 10 respectively, and a flow meter 42 is provided in the middle of the gas supply pipe 40 on the upstream side. It has been. The above-described supply gas is introduced into the gas supply pipe 40 by using equipment in the factory. The downstream end of the gas supply pipe 40 is connected to a supply connection pipe 20 shown in FIG.

 The plasma generation unit 60 receives power supply from the power supply 50 and generates plasma under atmospheric pressure or a pressure near the atmospheric pressure. As shown in FIG. 11, this plasma generating section 60 is provided with a dielectric, for example, a porous insulator 64 between a pair of electrodes 62 a and 62 b, so that each electrode 6 2a and 62b are arranged facing each other. A power supply 50 is connected to one electrode 62a, the other electrode 62b is grounded, and a relatively low frequency AC voltage or DC voltage of 50 kHz or less is applied between the electrodes. You. The power supply 50 applies a relatively low-frequency AC voltage or DC voltage of 50 kHz or less, preferably 0 to 50 kHz, to the pair of electrodes 62 a and 62 b. It has a plug 52 that plugs into the outlet.

 The reason why the power supply 50 outputs an AC voltage having a relatively low frequency is as follows.

That is, in order to generate atmospheric-pressure plasma, a large amount of helium gas He, which is relatively easy to generate plasma, was required. In this case, mark between the pair of electrodes. The frequency of the applied AC voltage could be set to the commercial frequency of 13.5.6 MHz. However, without using relatively expensive helium gas, atmospheric pressure plasma cannot be generated at an AC voltage of 13.56 MHz, which is a commercial frequency, in an atmosphere such as nitrogen and oxygen or compressed air. However, in the case of low-frequency AC voltage, the peak-to-peak voltage can be increased, and as a result, it is estimated that energy that contributes to plasma generation can be secured. Therefore, by applying an AC voltage or a DC voltage having a relatively low frequency of 0 to 50 kHz to the pair of electrodes, the atmospheric pressure plasma can be generated stably.

 Moreover, it is possible to generate plasma stably at or near atmospheric pressure using inexpensive nitrogen and oxygen or compressed air.

 An exhaust pipe 70 for forcibly exhausting the processing gas exposed to the lead frame 12 is provided inside the body 32 of the surface treatment unit 30. The exhaust pipe 70 in the surface treatment unit 30 is connected to an exhaust connection pipe 24 shown in FIG.

 Further, the exhaust pipe 70 is provided with a purifying means for purifying the processing gas, for example, a catalyst 80. Here, NO x is present in the processing gas exposed to the object. This NO x contributes to the surface treatment of the lead frame 12 of the IC 10, but NO x that did not contribute to the surface treatment or the reaction products newly generated by the reaction during the treatment are exhausted. . The exhaust gas is brought into contact with the catalyst 80 to chemically purify the processing gas. Moreover, the catalyst can be discarded without special treatment.

 In particular, if activated carbon having, for example, an adsorption function is used, exhaust components can be adsorbed on activated carbon. This activated carbon can be incinerated and discarded. As described above, when activated carbon is used, the running cost can be reduced as compared with the case where CF 3 is conventionally used as a processing gas and alumina is used as a trapping means.

 (Surface treatment method using the surface treatment unit in Fig. 10)

In the embodiment shown in FIG. 10, the supply gas is introduced into the gas supply pipes 40 of the surface treatment unit 30 by using the equipment arranged in the factory. The flow rate of this supply gas is adjusted by a flow meter 42 provided in the gas supply pipe 40 in the middle. The supply gas whose flow rate has been adjusted is introduced into the plasma generator 60. A pair of electrodes 62 a and 62 b provided in the plasma generating section 60 have a relatively low frequency of 10 to 50 kHz. An AC voltage having a wave number is applied.

 In the plasma generating section 60, the supplied gas is excited and decomposed, and becomes a processing gas containing nitrogen oxides. The processing gas derived from the gas supply pipe 40 of the surface treatment unit 30 is supplied to the IC 10 from the supply section 22 via the supply connection pipe 20 connected to the surface treatment unit 30. Exposure to the surface. Thereby, the lead frame 12 of IC 10 is surface-treated.

 On the other hand, the processing gas exposed to the lead frame 12 is introduced into the inside of the surface treatment unit 30 via the exhaust connection pipe 24. In the surface treatment unit 30, the above gas is guided to the catalyst 80 via the exhaust pipe 70.

 In addition, in order to generate the processing gas containing water, in addition to the processing gas generating section 600 shown in FIG. 9, the gas supply pipe 658a is provided with a steam mixing pipe as shown in FIG. What is necessary is just to add the structure which contacts the pure water 660 in the vessel 609. The supply gas led to the gas supply pipe 658a in FIG. 12 is led into pure water, and is brought into direct contact with the pure water and then sent out as a gas containing water. In this case, it is expected that the concentration of water in the gas to be sent out can be increased, and efficient surface treatment can be performed.

 Further, as shown in FIG. 13, the number of gas supply pipes for guiding the supply gas from the gas output section 6 19 is one, and the supply gas guided from the gas supply pipe 6 58 a via the valve 6 63 is provided. May be passed through pure water.

 Further, the steam mixer of the processing gas generator shown in FIGS. 9 and 12 can be mounted in the surface treatment unit 30 shown in FIG.

 Next, various supply gases are excited and decomposed by plasma discharge to generate nitrogen oxide processing gas, and the components contained in the exhaust gas after exposure to the workpiece are shown in Table 1. Show.

(Hereinafter the margin) 【table 1】

 In Table 1, all of Experiments 1 to 4 are of this example, and the types of electrodes Α and Β will be described later.

First, Experiment 3 and Experiment 4 are compared. The processing gas of the compressed air containing water used in Experiment 3 generated more Ν 〇 _2— than the processing gas consisting of only the compressed air used in Experiment 4, and the wettability was higher in Experiment 3 Turned out to be good. Here, NO- in the processing gas to be exposed to the workpiece, tends to NO ₂ by reduction of oxides of the workpiece surface, the wettability of the solder the more NO ₂ larger amount is improved in the exhaust gas considered Can be That is, the generation of a large amount of NO ₂ promotes the reduction of the oxide present on the surface of the lead frame 12, and can enhance the wettability of the lead frame 12.

 Next, Experiment 1 and Experiment 3 are compared assuming that the same processing gas is used but the electrodes are different.

In this comparison, the amount of N 0 ₂ — and N 0 ₃ generated in Experiment 3 using the B-type electrode was larger than the amount generated N 0 ₂ — and N 0 ₃ — in Experiment 1 using the A-type electrode. It was found that in Experiment 3, the wettability of the solder was more improved.

 Here, a schematic configuration of the A type electrode used for the electrode under the plasma condition is shown in FIG. 14, and a schematic configuration of the electrode of the B type is shown in FIG.

The A-type electrode in FIG. 14 is a pair of electrodes composed of an electrode 65 a connected to a power source 50 and an electrode 65 b grounded. A dielectric 64 is arranged between the pair of electrodes 65a and 65b. On the surface of the electrode 65a facing the dielectric 64, a concave portion 66 penetrating in the front-back direction of the drawing is formed. Atmospheric pressure or pressure near it Under the force, the power supply from the power source 50 causes the supply gas to pass through the concave portion 66, thereby generating a plasma discharge in the concave portion 66.

 The B-type electrode shown in FIG. 15 has a first electrode 67a and a second electrode 67b arranged with a dielectric 64 interposed therebetween. Unlike the electrodes of FIG. 14, the first and second electrodes 67a, 67b are respectively provided on each surface facing the dielectric 64, with the first and second concave portions 68a, 6 8b is formed. The first and second concave portions 68a and 68b penetrate in the front and back direction of the drawing. Further, the first and second concave portions 68a and 68b are formed at positions not opposed to each other. When the supply gas passes through one or both of the first and second concave portions 68a and 68b, plasma is generated in the first and second concave portions 68a and 68b, The feed gas is decomposed to produce a processing gas containing nitrogen oxides.

It is preferable to use an electrode of type B shown in the first 5 FIG reason the amount of generated N 0 _2, NO is large is as follows. In other words, the B-type electrode shown in Fig. 15 has a smaller stray capacitance between a pair of electrodes, and can use the power consumed by this stray capacitance as power for surface discharge. This is probably because the plasma density increases and the decomposition rate increases.

Thus, it is considered that the more NO and NO ₃ in the exhaust gas, the more the surface treatment for reducing oxides on the surface of the object was promoted. Therefore, it is considered that the surface treatment in Experiment 3 in which plasma discharge is generated using the B-type electrode has better wettability than the surface treatment in Experiment 1. Incidentally, the generated gas in Table 1, the process gas by purifying by touch contact with the catalyst, could be reduced to the order of 1 0 one ^{2 ~ 1 O ^ mg / m} 3.

 (Modified example of the surface treatment unit in Fig. 9)

 Next, another configuration of the surface treatment unit 30 of FIG. 9 will be described with reference to FIGS. 16 and 17. FIG.

The difference between the surface treatment unit 110 shown in Fig. 16 and the surface treatment unit 30 shown in Fig. 10 is that a gas supply pipe 41 is further mounted inside the housing 32. is there. Compressed air from a pump or nitrogen from a cylinder is introduced into the gas supply pipe 41 and supplied to the plasma generation unit 60. On the other hand, steam is supplied from the gas supply pipe 40. O 96 34

 20

Since it is supplied, surface treatment with high wettability can be performed.

 Further, as shown in FIG. 17, a gas output unit 6 19 can be mounted in advance in the surface treatment unit 120. The supply gas from the gas generation section 61 9 is led through the gas supply pipe 40, the flow rate is adjusted by the flow meter 42, and supplied to the plasma generation section 60.

 <About various evenings of the surface treatment unit>

 Next, various types of eves in which the shape of the above-mentioned surface treatment units 30, 100, and 110, or the shapes of the air supply connection pipe 20 and the exhaust connection pipe 24 connected thereto are changed. This will be described with reference to FIGS.

 (1) Line type

 The line-type surface treatment unit 160 shown in FIGS. 18 and 19 is provided at an upper position facing, for example, a plate-like work 500 conveyed by the conveyor line 14. . The surface treatment unit 160 has a supply / exhaust unit 162 at the lower part of the housing 161. The air supply / exhaust section 16 2 has a double-walled structure composed of an air supply pipe 16 4 and an exhaust pipe 16 6. In the present embodiment, the air supply pipe 164 is arranged at the center, and the exhaust pipe 166 is arranged around the air supply pipe 166. The lower end of the exhaust pipe 166 has an umbrella-like shape.

 When the work 500 is conveyed intermittently or continuously by the conveyor line 14, the work 500 faces the air supply / exhaust section 162 of the surface treatment unit, and the work 500 The surface will be surface treated. Thus, while the surface treatment unit 160 is fixed, a large number of works 500 can be continuously surface-treated on the entire surface of the work 500.

 (2) Stand type

The stand type surface treatment unit 200 shown in FIG. 20 has a housing 201 having a mountable bottom surface. The processing gas is introduced into the casing 201 as described above, and the exhaust gas is exhausted via the catalyst. The housing 201 is provided with an air supply connection pipe 210 and an exhaust connection pipe 230 extending upward. The air supply connection pipe 210 is bent and has an air supply part 220 opened at the lower end. An umbrella-shaped diffusion prevention plate 222 is provided around the air supply section 220 to prevent the diffusion of the processing gas. Have been killed. On the other hand, the exhaust connection pipe 230 has an umbrella-shaped exhaust suction portion 240 whose opening area increases upward as it faces upward.

 Then, as shown in FIGS. 20 and 21, at the time of processing the surface of the tip of the wire 250 from which the coating material at the end has been peeled off as a work, for example, The arranged tip portion 2 52 is arranged at a position immediately below the air supply portion 220. In this way, the distal end portion 250 of the wire rod 250 is subjected to the surface treatment with the processing gas derived from the air supply section 220, and the exposed processing gas is discharged to the exhaust suction section 240 and the exhaust connection pipe 2 It will be led to the catalyst in the housing 201 through 30.

 In this way, by using the stand type surface treatment unit 200, a local atmosphere of the treatment gas can be created in the air, and the workpiece such as the wire rod 250 can be easily surface treated. Becomes possible.

 (3) Rod type

 In the embodiment shown in FIGS. 22 and 23, the surface treatment unit 300 itself is constituted by a cylindrical housing 301 such as a soldering iron, for example. The air supply connection pipe 310 and the exhaust connection pipe 320 connected to the housing 301 have a double pipe structure, and the processing gas is processed by the inside air supply connection pipe 310. The exposed processing gas is led out toward the inside of the housing 301 from the exhaust connection pipe 320 on the outside. As shown in FIGS. 22 and 23, it is preferable that the distal end of the exhaust connection pipe 320 has an umbrella-like shape as shown in FIGS.

 As described above, if the surface treatment unit 300 itself is configured in a rod shape, it becomes possible to perform surface treatment of various works by manually operating the surface treatment unit 300 itself.

 (4) Tooth and evening type

The surface treatment unit 400 shown in FIGS. 24 and 25 has a slit-shaped insertion portion 4 on one surface of the housing 401, for example, on the upper surface thereof, into which a plate-shaped work 500 can be inserted. It has ten. An exhaust pipe 420 is connected to the slit-shaped insertion section 410. On the other hand, for example, on both side walls of the slit-shaped insertion portion 410, a processing gas supply pipe 430 having one end opened at the side wall is provided. According to this configuration, by inserting the plate-shaped work 500 into the slit-shaped insertion portion 410 provided on the upper surface of the housing 401, both sides of the work 500 can be inserted. The processing gas is sprayed more, so that both surfaces of the plate-like workpiece 500 can be simultaneously subjected to the surface treatment. In the case where only one surface of the work 500 is subjected to the surface treatment, the processing gas supply pipe 430 may be opened only on one side wall of the slit-shaped insertion portion 410.

 (5) Batch processing

 FIG. 26 shows an apparatus for processing a large number of workpieces in a batch system. This device connects the air supply pipe 20 and the exhaust pipe 24 connected to the above-mentioned surface treatment unit 30 (or 110 or 120) to a batch processing box 450. ing. The batch processing box 450 accommodates a large number of works 510 therein. The workpieces 50 to be batch-processed may be, for example, a TAB tape wound in a roll, in addition to the above-mentioned IC 10, wire rod 250, and plate-shaped workpiece 500.

 According to this batch processing type, it is possible to perform surface treatment on a large number of works 5 10 at a time. In addition, since the work surface-treated by the treatment method of the present invention can maintain the improved wettability of the solder for a relatively long time after the surface treatment, the work is stored until the soldering after the batch processing. Also, good soldering can be performed.

Claims

The scope of the claims

 1. A surface treatment method characterized by treating a surface of an object to be treated by bringing a treatment gas containing nitrogen oxide into contact with the surface of the object to be treated.

 2. In claim 1,

The process gas is, N ₂ 0, N0, N0 surface treatment method characterized by comprising either _2.

 3. In claim 1,

The process gas _{is, H 2 N 2 0 2,} HN 02, HN0 surface treatment method according to feature to include any acid _3.

4. In claim 2,

 A surface treatment method, further comprising the step of: generating a discharge in an atmosphere in which a supply gas containing oxygen atoms (〇) and nitrogen atoms (N) is supplied to generate the treatment gas.

 5. In claim 2 or 3,

 A surface treatment method, further comprising the step of generating a discharge gas in an atmosphere in which a supply gas containing oxygen atoms, nitrogen atoms, and hydrogen atoms is supplied to generate the processing gas.

 6. In Claim 4 or 5,

 A discharge is generated by exciting the supply gas by a pair of electrodes to which a low-frequency AC voltage or DC voltage of 50 kHz or less is applied at or near atmospheric pressure. Surface treatment method.

 7. In claim 6,

 The pair of electrodes has first and second electrodes disposed with a dielectric interposed therebetween, and the first and second electrodes are located on opposite sides of each surface facing the dielectric. First and second recesses are formed in the

 A surface treatment apparatus characterized in that the supply gas is introduced into at least one of the first and second recesses.

 8. In claim 2,

Heats the atmosphere in which the supply gas containing oxygen atoms (0) and nitrogen atoms (N) is supplied And a step of generating the processing gas.

 9. In Claim 2 or 3,

 A surface treatment method, further comprising: heating an atmosphere to which a supply gas containing oxygen atoms, nitrogen atoms, and hydrogen atoms is supplied to generate the treatment gas.

10. In claim 2,

 A surface treatment method further comprising the step of: irradiating light to an atmosphere supplied with a supply gas containing oxygen atoms and nitrogen atoms to generate the treatment gas.

 1 1. In Claim 2 or 3,

 A surface treatment method, further comprising: irradiating light to an atmosphere supplied with a supply gas containing oxygen atoms, nitrogen atoms, and hydrogen atoms to generate the treatment gas.

 1 2. In claim 4 or 8 or 10,

A surface treatment method, wherein oxygen (0 gas and nitrogen (N ₂ ) gas are supplied as the supply gas, and the nitrogen gas is also used as a carrier gas.

 1 3. In claim 5 or 9 or 11,

As the feed gas, oxygen (0 ₂₎ nitrogen which is also used as a gas and the carrier gas (N ₂₎ supply a gas and is contacted with water at least one at supply course of the oxygen gas and nitrogen gas A surface treatment method comprising:

 14. In claim 5 or 9 or 11,

 A surface treatment method, comprising supplying a nitrogen (N 2) gas as the supply gas, and bringing the nitrogen gas into contact with water during the supply.

 15. In claim 5 or 9 or 11,

 A surface treatment method comprising: supplying compressed air as the supply gas; and bringing the compressed air into contact with water during the supply.

 16. In claim 12 or 13,

 A surface treatment method, wherein the supply amount of the oxygen gas is set to 15% by volume or less.

17. In claim 12 or 13, A surface treatment method, wherein the supply amount of the oxygen gas is set to 10% by volume or less.

 18. In Claim 12 or 13,

 A surface treatment method, wherein the supply amount of the oxygen gas is 5 to 10% by volume.

 19 · In Claim 3,

 A surface treatment method, further comprising a step of electrolyzing an aqueous solution of a salt composed of an alkali metal and a nitrogen compound to generate the nitrogen compound.

2.0. In Claim 3,

H2N2O2, HN 02, HN0 surface treatment method characterized by any of the aqueous solution of ₃ by contacting the carrier gas further comprises the step of generating the processing gas. 21. In any one of claims 1 to 18,

 Forcibly exhausting the processing gas and the reaction product supplied toward the object to be processed;

 A step of trapping the processing gas and the reaction product during the evacuation.

 22. In any one of claims 1 to 21,

 The processing gas is brought into contact with the surface of the object to be processed to reduce an oxide on the surface of the object to be processed or to replace the oxide with a nitrogen oxide to improve the wettability of the solder on the surface. A surface treatment method characterized by improving.

 23. In claim 17,

 A surface treatment method, wherein the pair to be treated is a circuit board.

 19. In claim 17,

 A surface treatment method, wherein the object to be processed is an electronic component.

 20. In claim 17,

 A surface treatment method, wherein the object to be processed is an integrated circuit, and the surface to be processed is a bonding surface of the integrated circuit.

 21. In claim 17,

The surface treatment method, wherein the object to be processed is a wire to be soldered.

22. In claim 17,

 A surface treatment method, wherein the surface of the object to be processed is an electrode of a quartz oscillator.

23. NO, N0 _2, N _{2 〇, HN0 3, HN0 2, H} 2 N 2 0 one or selected from among ₂ leads the process gas containing a plurality of nitrogen oxide on the surface of the object to be processed process gas A surface treatment apparatus, comprising: a supply unit, for treating a surface of an object to be treated.

24. In claim 23,

A discharge is generated in an atmosphere in which a supply gas containing oxygen atoms (0) and nitrogen atoms (N) is supplied and connected to the processing gas supply means, and N〇, NO ₂ , A surface treatment apparatus further comprising a treatment gas generation means for generating any one of N ₂₀ .

25. In claim 23,

 A discharge is generated in an atmosphere in which a supply gas including an oxygen atom (0), a nitrogen atom (N), and a hydrogen atom (H) is supplied to the processing gas supply means, and the processing gas is supplied. A surface treatment apparatus further comprising a processing gas generation unit for generating the processing gas.

26. In claim 23,

Said processing are connected to gas supply means, an oxygen atom by heating the atmosphere in which the feed gas is supplied comprising a (◦) and nitrogen atom (N), which of N0, N0 _2, N ₂ 0 of the process gas A surface treatment apparatus further comprising a processing gas generating means for generating a gas.

 27. In claim 23,

 A processing gas connected to the processing gas supply means and heating an atmosphere supplied with a supply gas containing oxygen atoms (0), nitrogen atoms (N), and hydrogen atoms (H) to generate the processing gas A surface treatment apparatus further comprising a generation unit.

 28. In claim 23,

Connected to the process gas supply means, a feed gas containing the oxygen atom (0) and nitrogen atom (N) is irradiated with light in an atmosphere to be supplied, N0 of the process gas, N0 _2, N ₂ 0 A surface treatment apparatus further comprising a processing gas generation means for generating any one of the above.

29. In claim 23,

 The processing gas is generated by irradiating light to an atmosphere connected to the processing gas supply means and supplied with a supply gas containing oxygen atoms (0), nitrogen atoms (N), and hydrogen atoms (H). A surface treatment apparatus further comprising a treatment gas generation unit.

 30. In claim 23,

 A surface processing apparatus further comprising a processing gas generating means connected to the processing gas supply means and configured to electrolyze an aqueous solution of a salt comprising an alkali metal and a nitrogen compound to generate the processing gas.

3 1. In claim 23,

Said processing are connected to gas supply means, by contacting the _{H 2 N 2 0 2, HN0} 2, HN0 3 of one of the aqueous solution in the carrier gas, one of _{H 2 N 2 0 2, HN0} 2, HN0 3 And a processing gas generating means for generating the processing gas.