JP2005026167A - Plasma surface treatment device and its treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device allowing a user to execute a downstream (D) method and a planar (P) method by arbitrarily selecting one of them with the single device in accordance with the object and the purpose of plasma surface treatment; and to provide a method capable of remarkably reducing the consumption of gaseous nitrogen of a reaction gas in the D method. <P>SOLUTION: This device is equipped with: electrodes 4 and 5 of the D method oppositely disposed so as to interpose a supply passage of the reaction gas to a board W; electrodes 4, 6 and 7 oppositely disposed so as to interpose the board W; and is so structured that a high-frequency voltage can be supplied to the electrodes of the D method and the electrodes of the P method according to the object and the purpose of the surface treatment by changing over it. In addition, gaseous nitrogen mixed with oxygen at a volume ratio of 0.01-0.25% or air at a volume ratio of 0.1-2.5% is used for the reaction gas of the D method. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a plasma surface treatment apparatus, and more particularly, to a substrate to be treated such as an FPD (flat panel display), an FPD filter, a printed board, a film-like substrate, a semiconductor wafer, a photomask, and a solar cell substrate. The present invention relates to a plasma surface treatment technique for performing surface treatment with plasma under a pressure near atmospheric pressure.

  An FPD manufacturing process and a semiconductor device manufacturing process such as an IC are advanced by repeatedly forming a thin film of an organic or inorganic material on a substrate such as a glass substrate or a semiconductor wafer.

  In these formations, surface modification as a pretreatment is required. This includes, for example, resist residue removal before the resist coating, development before and after development, wet etch pretreatment, and wet cleaning pretreatment.

  This pretreatment is generally performed by light cleaning with a UV lamp or an excimer lamp. However, it has been necessary to replace expensive lamps several times a year due to the lamp life, and this has been a factor in increasing product manufacturing costs due to the burden of lamp costs and the reduction in operating rate associated with lamp replacement.

  Moreover, when using the said lamp | ramp, the synthetic quartz board with which the light irradiation window of the lamp house lower part is clouded by the adhesion of the product by the outgas generated from the to-be-processed substrate surface by an ozone effect. The synthetic quartz plate has a built-in heater for preventing fogging, but in order to ensure the desired performance, several cleanings are required in 1 to 3 months, and at least once every 2 years or 2 It is necessary to exchange more than once. This synthetic quartz plate is expensive and has the same manufacturing cost problem as described above.

  As described above, surface modification using a UV lamp or excimer lamp leads to an increase in manufacturing cost. Therefore, surface modification using a plasma surface treatment apparatus has been attempted.

  In this method, the surface of a substrate to be processed is reformed with a plasma reaction gas under a pressure close to atmospheric pressure. The downstream method (hereinafter referred to as D method) and the planar method (hereinafter referred to as P method). There is. In the D method, a reaction gas is converted into plasma through a counter electrode to which a high-frequency voltage is applied, and this is sprayed and supplied to a substrate to be processed to perform surface modification. In the P method, high-frequency power is applied between counter electrodes arranged so as to sandwich a substrate to be processed, and the supplied reaction gas is converted into plasma and directly applied to the substrate to be processed to perform surface modification.

  As the reaction gas, a rare gas, particularly He gas is often used. For the purpose of reducing running costs, the present applicant has considered using nitrogen gas as a reaction gas instead of expensive noble gas. Nitrogen gas is inexpensive, but in order to obtain a predetermined processing capacity, the flow rate needs to be considerably higher than that of rare gas. Further, even when compared with the amount of high-frequency power used for plasmification under atmospheric pressure, nitrogen gas requires more power than noble gas. The amount of power used in the case of nitrogen gas is four times that of Ar gas, which is the largest amount of power used compared with other He, Kr, and Xe gases among rare gases.

  That is, in order to use in a production line, it is necessary to reduce both the amount of nitrogen gas used and the amount of power used. Based on this premise, when nitrogen gas was used as a reaction gas and the D-type and P-type plasma surface treatment apparatuses were compared by experiments, the following results were obtained.

  The surface modification by the D-type plasma surface treatment apparatus has a low treatment efficiency. This is because the lifetime of the plasma active species is abnormally short and part of the generated plasma disappears during the injection supply time. For this reason, in order to ensure processing efficiency that matches the feed rate of the production line, it is necessary to increase the amount of reaction gas used and the power density applied to the electrodes, or to use a plurality of plasma generators in combination. there were. For this reason, an increase in running cost and an increase in equipment cost when installing a plurality of units have been problems. This treatment efficiency is particularly problematic for organic surfaces such as ITO (transparent conductive film).

  When surface modification is performed by a P-type plasma surface treatment apparatus, the generated plasma acts directly on the substrate to be treated, so that the surface modification efficiency is high. In order to obtain performance equivalent to or better than the P method by the D method, the power density applied to the electrode portion must be 10 times or more that of the P method, and the reaction gas must be used twice or more of the P method.

  However, since the P method generates plasma by applying a high-frequency high-frequency voltage to the electrode gap, it has a strong effect on the surface of the substrate to be processed. For example, in a TFT liquid crystal panel or a semiconductor device manufacturing process, a transistor such as an FET Depending on the processing conditions, there is a possibility that damage such as gate damage of the transistor is caused and the yield is lowered.

  As described above, the D method and the P method have merits and demerits, and it is difficult to determine which method of plasma surface treatment apparatus is used. This is particularly difficult when the surface treatment targets are diverse depending on whether organic or inorganic materials, transistor patterns are present, or the like. And a problem arises in the operation after the introduction of the apparatus.

In addition, the surface treatment by the D method or the P method is used for adhesion improvement or drying by removing residues in addition to the surface modification, and the advantages and disadvantages of the D method and the P method are as follows. This also appears in the same way. Further, when a rare gas is used as a reactive gas, the advantages and disadvantages of the D method and the P method appear as the same tendency.
JP 2002-110639 A

  Accordingly, an object of the present invention is to provide an apparatus in which a user can arbitrarily select and execute a surface treatment of the D method and the P method with a single device in accordance with the object and purpose of the surface treatment.

  Another object of the present invention is to provide a method of reducing the running cost by greatly reducing the amount of reaction gas used in the D-type plasma surface treatment method.

  The present invention is an apparatus for performing a surface treatment of a substrate to be processed with a reaction gas converted into a plasma under a pressure near atmospheric pressure, and is disposed so as to face the supply path of the reaction gas to the substrate to be processed. A pair of one or more D-type electrodes for supplying plasmaized reaction gas to the substrate to be processed and a pair of one or more electrodes arranged to face the substrate to be processed so that the plasmaized reaction gas acts directly on the substrate to be processed. A P-type electrode is provided, and a high-frequency voltage can be switched and supplied to the D-type electrode and the P-type electrode according to the object and purpose of the surface treatment.

  The D-type electrode and the P-type electrode can have a structure in which some of the electrodes are shared.

  As a structure sharing a part of the D-type electrode and the P-type electrode, a pair of P-type electrodes arranged so as to sandwich the substrate to be processed and a reaction gas supply path to the substrate to be processed are formed. As described above, there is a structure in which an electrode disposed opposite to one side surface of the electrode is provided, and one of the electrodes and an electrode disposed opposite to the electrode are D-type electrodes.

  The above-mentioned plasma surface treatment apparatus has a usage method in which surface treatment is performed with a D-type electrode when it is desired to minimize damage to the surface of the substrate to be processed, and when the treatment efficiency is important, the surface treatment is efficiently performed with a P-type electrode. Is possible.

  In the structure in which the electrodes are arranged opposite to the side surfaces of the P-type electrodes to form the D-type electrodes, the opposed electrodes are electrically neutralized, and a high-frequency voltage is applied to the P-type electrodes, A method is possible in which a partial pressure of the applied high-frequency voltage is induced to the electrodes arranged oppositely, the D-type electrode is operated by this partial pressure, and the reaction gas is pre-plasmaized and supplied to the P-type electrode. It is.

  In the D-type surface treatment method in which the plasma-treated reaction gas is jetted and supplied to the substrate to be treated to perform surface treatment, as the reaction gas, nitrogen gas mixed with 0.01 to 0.25% oxygen, or Nitrogen gas mixed with 0.1 to 2.5% air can be used.

  In the present invention, a plurality of plasma surface treatment apparatuses are installed with a configuration in which a D-type electrode and a P-type electrode are juxtaposed, and a high-frequency voltage can be switched and supplied according to the object and purpose of surface modification. Even if it is not, the user can arbitrarily select and implement the surface treatment of the P method and the D method with one apparatus. Then, the user can operate using the advantages of the P method and the D method.

  If a part of the D-type electrode and the P-type electrode is shared in the above configuration, the apparatus can be miniaturized and the cost can be reduced.

  The above-mentioned plasma surface treatment apparatus is used to perform surface treatment with a D-type electrode when it is desired to minimize damage to the surface of the substrate to be processed, and to efficiently perform surface treatment with a P-type electrode when importance is placed on the treatment efficiency. Then, running costs can be reduced while suppressing a decrease in product yield.

  As described above, in order to share a part of the D-type electrode and the P-type electrode, the electrode is arranged opposite to the side surface of the P-type electrode to form the D-type electrode. When the electrode is electrically neutral, it is possible to induce a partial pressure of the high-frequency voltage applied to the P-type electrode. Then, this partial pressure makes it possible to work with the D-type electrode to make the reaction gas into plasma. The plasma reaction gas is supplied to the P-type electrode, and the plasma concentration at the P-type electrode can be increased to improve the processing performance.

  In the D-type surface treatment method, as a reaction gas, nitrogen gas mixed with 0.01 to 0.25% oxygen, or nitrogen gas mixed with 0.1 to 2.5% air When used, the amount of nitrogen gas used can be halved to obtain the same processing performance, and the running cost can be reduced.

  FIG. 1 is a perspective view showing an appearance of a plasma surface treatment apparatus 1 according to an embodiment of the present invention. The plasma surface treatment apparatus 1 is arranged in the middle of a conveyor 2 on which a substrate W, which is an object to be processed, is placed and carried, and the substrate W is passed through the slit-shaped opening 3 to perform surface treatment with plasma.

  The internal structure of the plasma surface treatment apparatus 1 will be described with reference to a cross-sectional view shown in FIG. In the figure, 4 and 5 are a pair of electrodes opposed to each other at equal intervals, and 6 and 7 are electrodes arranged opposite to the side surface of the electrode 4. These electrodes are long in the direction orthogonal to the paper surface in order to obtain an effective processing width corresponding to the width of the conveyor 2 shown in FIG. 1, and are manufactured by processing a metal such as aluminum, and are water-cooled (not shown) inside. A cavity is formed and covered with a solid dielectric 8.

Further, the widths a, b, and c of the portions related to the plasma generation of the electrodes 4, 5, 6, and 7 are determined from the optimum power consumption per unit area of these portions. When the flow rate of the reaction gas and the high frequency power are constant, 7 to 15 watts per 1 cm ² are desirable. This is because even if an electric power higher than that is applied to obtain a high plasma density, it is converted into heat and is not very efficient.

  An insulating liquid, which is a cooling liquid, is circulated and pumped through a cooling liquid supply pipe (not shown) into the water cooling cavity to suppress heat generation of the electrodes. The insulating liquid is, for example, pure water or city water, ethylene glycol, galden, fluorinate, etc., and the cooling temperature is kept at, for example, 100 ° C. or less so that the substrate W is not thermally damaged. I have to.

  The electrodes face each other through the solid dielectric 8, and the facing surface of the solid dielectric 8 becomes a discharge surface for generating plasma.

  The reason why the electrode is covered with the solid dielectric 8 is to prevent the substrate W from being contaminated by the electrode metal by isolating the electrode from the outside air and the gas used. The relative dielectric constant of the solid dielectric 8 is preferably about 9 to 13 in order to concentrate the electric field in the discharge gap, and the coating thickness t of the solid dielectric from the metal electrode is preferably 1 mm to 10 mm.

  The electrodes 4 and 5 face each other so as to sandwich the substrate W that is the object to be processed, thereby forming parallel plate electrodes. This is a planar (P) type electrode that directly causes the generated plasma to act on the substrate W.

  The electrodes 6 and 7 are disposed opposite to each other on both sides of the substrate 4 on the introduction side and the discharge side of the substrate 4 so as to form a supply path for the reaction gas to the substrate W. Reference numeral 7 denotes a downstream (D) type electrode.

  Since the facing distance L between the electrodes 4 and 6 and the electrodes 4 and 7 serving as the reaction gas supply paths 20 and 21 greatly changes the reforming performance, the excited state of the passing reaction gas is observed using an emission spectrometer. To decide.

  This depends on the type of reactive gas, its flow rate, and the magnitude of the high-frequency voltage, and is affected by the distance d to the substrate W. In the structure of this embodiment, the reactive gas is nitrogen, When the interval at which the absorption wavelength becomes the highest was obtained, it was found that the interval L is preferably 0.5 mm to 5 mm.

  These electrodes 4, 5, 6, 7 are covered with upper and lower electrode section covers 9, 10, and cavities 11, 12 for making the reaction gas pressure uniform are formed inside. Connected to the cavities 11 and 12 are supply pipes 13 and 14 for introducing the reaction gas near the atmosphere. Exhaust pipes 15, 16, 17 and 18 for discharging the reaction gas used for the processing are also attached to the electrode cover 9 and 10.

  Further, in order to switch these electrodes 4, 5, 6, and 7 as P-type electrodes and D-type electrodes, a high-frequency power source RF and a change-over switch circuit SW are provided.

  The high-frequency power supply RF supplies high-frequency power to the electrode via a step-up transformer, and a PLL that causes the high-frequency frequency to follow fluctuations in the resonance frequency of a parallel resonance circuit that occurs when the secondary side of the step-up transformer is connected to the electrode. It has a circuit.

  The changeover switch circuit SW is a two-circuit interlocking switch and has three changeover contacts P1, P2, and D.

  When applied to the switching contact P1, high-frequency power is applied between the electrodes 4 and 5, and at the same time, the potentials of the electrodes 6 and 7 are kept at the same potential of the electrode 4. This is for operating as a P system.

  At this time, the reaction gas uniformized by entering the cavity 11 from the reaction gas supply pipe 14 is supplied between the electrode 4 and the electrode 6 and between the electrode 4 and the electrode 7. 21, the pressure is close to the atmospheric pressure, and is discharged from above into the space through which the substrate W passes.

  Further, the reaction gas that has entered the cavity 12 from the reaction gas supply pipe 13 and is made uniform passes through the reaction gas supplies 22 and 23 formed by the partition walls 24 on both sides of the electrode 5 and reaches a pressure close to atmospheric pressure. Thus, it is emitted from below into the space through which the substrate W passes.

  In this state, high-frequency power is applied between the electrode 4 and the electrode 5, so that discharge occurs and plasma is generated. This acts directly on the substrate W from the upper side and the lower side, so that simultaneous processing on both the front and back surfaces can be performed efficiently. An auxiliary discharge also occurs between the electrodes 6 and 7 and the electrode 5 that are kept at the same potential as the electrode 4, and an efficient surface treatment is performed by the plasma generated thereby.

  When being applied to the switching contact P2, a high frequency voltage is applied between the electrodes 4 and 5, and the electrodes 6 and 7 are kept electrically neutral. This is also for the operation as the P system, but the action of the electrodes 6 and 7 is different from that when P1 is applied.

  Since the electrodes 6 and 7 are kept neutral, when a high-frequency voltage is applied between the electrodes 4 and 5, a partial pressure is generated between the electrodes 4 and the electrode 4 by induction. For this reason, when the reaction gas passes through the reaction gas supply paths 20 and 21 formed between the electrode 4 and the electrode 6 and between the electrode 4 and the electrode 7, a discharge occurs at this partial pressure to generate plasma. . The reaction gas partially converted into plasma is discharged from the upper side into the space through which the substrate W passes. At this time, a discharge is generated between the electrodes 4 and 5 to generate plasma in the upper and lower spaces of the substrate W. Since plasma formation is performed twice on the upper side of the substrate W, the plasma density in the upper space can be increased, and the reforming performance for the upper surface of the substrate W is improved as compared with the case where it is put into P1.

  When applied to the switching contact D, a high frequency voltage is applied to the electrodes 4 and 6 and the electrodes 4 and 7, and the electrode 5 is neutral. This is for operating as a D system.

  At this time, since the process for the lower surface of the substrate W is not performed, the reaction gas is supplied only from the supply pipe 14. The reaction gas that has entered the cavity 11 and is made uniform passes through the supply paths 20 and 21 and is discharged from above into the space through which the substrate W passes at a pressure close to atmospheric pressure.

  At this time, since the high frequency voltage is applied to the electrodes 4 and 6 and the electrodes 4 and 7 facing each other with the supply paths 20 and 21 interposed therebetween, discharge occurs and plasma is generated. Then, the plasma reaction gas is ejected from above into the space through which the substrate W passes, and surface treatment is performed. Thus, when it is put into D, the surface treatment is performed only on the upper surface of the substrate W.

  The electrode structure of the plasma surface treatment apparatus of the present invention may be different from that shown in FIG. That is, the electrode of the present invention is designed by combining a pair of or more D-type electrodes and a pair of or more P-type electrodes, if necessary, in part, and combining them.

  For example, as one design example, the electrode 4 in FIG. 2 can be divided into a plurality of parts in the moving direction of the substrate W. In this case, the divided electrode is used as a P-type electrode by applying a high-frequency voltage with the same polarity, and the D-type electrode is applied by applying a high-frequency voltage with different adjacent electrodes as different polarities. Use as

  Since the circuit for switching and supplying the high-frequency voltage in each design differs depending on the electrode structure and usage mode, the change-over switch SW is appropriately designed according to them.

  When the plasma surface treatment apparatus 1 is operated as the D method, there is still a problem that the consumption amount of the reaction gas is large and the running cost is high.

  Therefore, a plasma surface treatment method capable of reducing the cost by reducing the consumption amount of the reaction gas will be described below.

This method is a D-type surface treatment method in which 0.01 to 0.25% oxygen is mixed into nitrogen gas or 0.1 to 2.5% air is mixed into nitrogen gas as a reaction gas. It uses the mixed material.
In this way, the fact that the consumption of reactive gas can be reduced and the cost can be reduced will be described with experimental data.

  3 to 5 show the results of surface modification experiments using the FPD bare glass substrate using the plasma surface treatment apparatus 1 described above.

  FIG. 3 shows the amount of gas ejected to the substrate and the result obtained by using the three types of nitrogen gas alone, nitrogen gas mixed with oxygen, and nitrogen gas mixed with air as the reaction gas in the D method. It shows the relationship of contact angle improvement. Incidentally, making the contact angle 10 ° or less is one of the target values for achieving surface modification.

  As is clear from this figure, in the case where oxygen or air is mixed into nitrogen gas, the contact angle can be reduced to 5 ° or less at a flow rate of 1/7 compared with the case of nitrogen gas alone. .

  From this data, it can be seen that if oxygen or air is mixed into nitrogen gas, the amount of reaction gas used in the D method can be greatly reduced. This is because the same effect can be obtained even in an apparatus dedicated to the D system.

  Next, FIG. 4 shows the surface modification dependency of oxygen and air addition amounts in the D method. The effect of improving the contact angle with respect to the amount of added gas differs between when oxygen is added to nitrogen gas and when air is added.

  When nitrogen gas is used as the reaction gas and the target value is a contact angle of 10 ° or less, in the case of oxygen, 0.01 to 0.25% oxygen may be mixed in by volume ratio. On the other hand, in the case of air, 0.1 to 2.5% of air may be mixed in by volume ratio.

  FIG. 5 shows the amount of reaction gas used to obtain the same contact angle (10 °) as a result of surface modification with respect to the size of the substrate to be processed, nitrogen gas alone, nitrogen gas mixed with oxygen, The measurement results for three types of nitrogen gas mixed with air are shown.

  For nitrogen gas mixed with oxygen or air, the required flow rate is proportional to the size of the substrate, but with nitrogen gas alone, the efficiency decreases as the substrate size increases, and the amount of reaction gas used per unit area Was found to increase.

  In recent years, since the size of the substrate to be processed tends to increase, the data of FIG. 5 shows that the method of the present invention is useful in manufacturing a plasma surface treatment apparatus corresponding to this.

  The present invention provides a surface by plasma under a pressure near atmospheric pressure on a substrate to be processed such as an FPD (flat panel display), an FPD filter, a printed board, a film substrate, a semiconductor wafer, a photomask, or a solar cell substrate. The treatment can be used to perform modification treatment for imparting hydrophilicity or hydrophobicity, improvement of adhesion by removing residues, drying, and the like.

It is a perspective view which shows the external appearance of the plasma surface treatment apparatus which is one Embodiment of this invention. It is sectional drawing which shows the internal structure of the plasma surface treatment apparatus of FIG. It is a figure which compares and shows the improvement effect of the contact angle when oxygen or air mixes with nitrogen gas when surface modification is performed by the D method. It is a figure which compares and shows the improvement effect of the contact angle with respect to the addition amount of oxygen or air with respect to nitrogen gas, when surface modification is carried out by D method. It is a figure which compares and shows the usage-amount of nitrogen gas when not adding oxygen or air with respect to to-be-processed substrate size expansion when surface modification is carried out by D method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plasma surface treatment apparatus 2 Conveyor W The board | substrate which is a to-be-processed object 3 The opening of a plasma surface treatment apparatus 4 The electrode shared by a planar (P) system and a downstream (D) system 5 The electrode of a planar (P) system 6,7 Downstream (D) type electrode 8 Solid dielectric a, b, c Width of the part relating to plasma generation L Electrode spacing 9, 10 Electrode cover 11, 12 Cavity 13, 14 Reaction gas supply tube 15, 16, 17, 18 Exhaust pipe RF high frequency power supply SW switch circuit P1, P2, D switch contact

Claims (7)

An apparatus for performing a surface treatment of a substrate to be processed with a plasma reaction gas under a pressure near atmospheric pressure,
A pair of downstream-type electrodes arranged to face the supply path of the reaction gas to the substrate to be processed, and to inject and supply the plasmad reaction gas to the substrate to be processed;
A pair of or more planar electrodes that are disposed so as to sandwich the substrate to be processed and directly act on the substrate to be processed by the plasma reaction gas,
A plasma surface treatment apparatus, wherein high-frequency voltage is switched and supplied to a downstream electrode and a planar electrode according to the purpose of the surface treatment.   2. The plasma surface treatment apparatus according to claim 1, wherein a part of the electrode is shared by a downstream type electrode and a planar type electrode.   A pair of planar electrodes arranged opposite to each other to sandwich the substrate to be processed, and electrodes disposed opposite to one side surface of the electrode so as to form a reaction gas supply path to the substrate to be processed; 3. The plasma surface treatment apparatus according to claim 2, wherein one of the electrodes and an electrode disposed opposite to the electrode are downstream electrodes.   When the plasma surface treatment apparatus according to any one of claims 1 to 3 is used and surface damage of the substrate to be treated is to be reduced as much as possible, the surface treatment is performed with a downstream electrode, and treatment efficiency is emphasized. A plasma surface treatment method characterized in that surface treatment is sometimes performed with a planar electrode.   Using the plasma surface treatment apparatus according to claim 3, the electrodes arranged opposite to each other are electrically neutralized, and a high frequency voltage is applied to a pair of planar electrodes, whereby the electrodes applied to the electrodes arranged opposite to each other are applied. A plasma surface treatment method characterized by inducing a partial pressure of a high-frequency voltage, operating a downstream electrode by this partial pressure, and plasmaizing a reactive gas in advance and supplying the plasma to a planar electrode. In a downstream type plasma surface treatment method in which a reaction gas having a pressure near atmospheric pressure is converted into plasma through a counter electrode to which a high-frequency voltage is supplied and sprayed onto a substrate to be processed to perform surface treatment.
A plasma surface treatment method characterized by using nitrogen gas mixed with 0.01 to 0.25% oxygen as a reaction gas. In a downstream plasma surface treatment method in which a reaction gas having a pressure near atmospheric pressure is converted into plasma through a counter electrode to which high-frequency power is supplied, and sprayed onto a substrate to be processed to perform surface treatment.
A plasma surface treatment method characterized by using nitrogen gas mixed with 0.1 to 2.5% air as a reaction gas.

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