JP2003324064A - Development method and developing equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent insoluble substances floating in a developer from attaching to the surface of a wafer. <P>SOLUTION: An electrode board capable of applying a predetermined voltage with predetermined polarity is provided on the upper surface of a spin chuck which holds a wafer. Then, immediately before the developer is supplied to the wafer held on the upper surface of the spin chuck, the predetermined voltage is applied to the electrode board and the electrode board is charged with the same polarity as that of the ζ-potential of the insoluble substances which precipitate in the developer by the supply of the developer or the like. The electrons within the wafer are electrostatically induced by the electrode board and the ζ-potential of the wafer surface is charged so as to have the same polarity as that of the ζ-potential of the insoluble substances. As a result, the insoluble substances and the wafer surface, which have the same polarity, repel each other and the insoluble substances are prevented from attaching to the wafer surface. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate developing method and a substrate developing apparatus.

[0002]

2. Description of the Related Art In a photolithography process in a semiconductor device manufacturing process, for example, a resist solution which is a photosensitive resin is applied to the surface of a wafer and a resist film is formed on the wafer. An exposure process for exposing a predetermined circuit pattern on a wafer, a developing process for supplying a developing solution to the exposed wafer to dissolve the resist film in the exposed portion, and the like are performed.

In the above-mentioned development process, a strongly alkaline developing solution is supplied onto the wafer, and the developing solution is puddle on the wafer. Then, this liquid-filled state is maintained for a predetermined time, and the wafer is statically developed. In this static development, a part of the resist film, that is, the exposed portion which has been made soluble in the developing solution by exposure is dissolved in the developing solution. When the static development for a predetermined time is completed, the wafer is rotated, a cleaning liquid, for example, pure water is supplied onto the wafer, and the developing liquid is replaced with pure water. After that, the supply of pure water is stopped, the wafer is shaken off and dried, and a series of development processing is completed.

[0004]

However, in the above-mentioned static development, the resist film of all the exposed areas is not properly dissolved in the developing solution, so that the exposed areas and the exposure amount are insufficient. A so-called insolubilized product insoluble in the developer is deposited in the developer from the boundary between the exposed portion and the unexposed portion where the amount is insufficient.

The particles of the insoluble material dispersed in the liquid are usually charged, and the charge state (surface potential) on the surface of the particles is generally evaluated by the zeta potential. The zeta potential represents the electric potential near the surface of the particle, and strictly speaking, the electric potential at a part (sliding surface) of the diffusion layer around the fixed layer formed around the particle in the liquid, based on the infinite distance of the particle. Is. Since the zeta potential of a particle depends on the polarity of the liquid around the particle, the number of ions, that is, p of the liquid
Affected by H value. Generally, in alkaline liquids, since there are many anions, the zeta potential tends to be low. In acidic liquids, since there are many cations, the zeta potential tends to be high.

According to the experiments conducted by the inventor, it has been confirmed that the zeta potential of the insoluble matter suspended in the strong alkaline developing solution in the above-mentioned developing process is negative in the developing solution. It has also been confirmed that the zeta potential on the wafer surface that comes into contact with the developer is also negatively charged.

When pure water is supplied onto the rotated wafer as described above and the developing solution is replaced with pure water,
It has also been confirmed by the inventor that the pH value of the developer sharply decreases, and as a result, the zeta potential of the insoluble material increases toward 0 mV. When the absolute value of the zeta potential of the insolubilized product becomes small in this way, the electrostatic repulsion force between the insolubilized product and the wafer surface weakens, and instead the intermolecular force becomes relatively strong, so that the insolubilized product adheres to the wafer surface. . In particular, when the absolute value of the zeta potential of the insoluble material becomes small, the insoluble materials agglomerate with each other and grow into particles having a larger intermolecular force, so that they easily adhere to the wafer.

As a result, the insoluble matter adhering to the wafer cannot be easily removed even by cleaning the wafer, and the remaining insoluble matter causes development defects. Further, in order to clean and remove the insoluble matter adhering to the wafer surface, it is necessary to continue supplying pure water to the wafer for a long time, and as a result, the total development processing time becomes long, resulting in a decrease in wafer processing throughput. Was there.

The present invention has been made in view of the above points, and prevents insoluble matter floating in a developing solution from adhering to the surface of a substrate such as a wafer, thereby reducing development defects and developing processing time. It is an object of the present invention to provide a development processing method and a development processing apparatus capable of realizing the reduction of the above.

[0010]

According to a first aspect of the present invention, there is provided a development processing method for developing a substrate by supplying a developing solution onto a resist film formed on the surface of the substrate. The development processing method is characterized in that the development processing is performed by controlling the zeta potential of the above to a predetermined potential having the same polarity as the zeta potential of the insoluble matter floating in the developing solution.

According to the present invention, since the zeta potential on the surface of the substrate is controlled to a predetermined potential having the same polarity as the zeta potential of the insolubilized material in the developing solution, a sufficient electric potential is maintained between the insolubilized material and the surface of the substrate. It can generate a strong repulsive force. Therefore, the insoluble matter can be prevented from adhering to the substrate, and the development defects caused by the adhering can be reduced. In addition, the cleaning time can be shortened because the insoluble matter does not adhere, and the development processing time can be shortened. The surface of the substrate includes the base of the resist film and the antireflection film, and the base may be an oxide film,
Other types of membranes may be used. Further, the zeta potential on the substrate surface may be controlled so that the absolute value of the zeta potential on the substrate surface is 30 mV or more.
The “insoluble matter” may be deposited from the resist film, may be originally present in the developing solution, or may be entered into the developing solution from the outside.

In the developing process, a first step of piling a developing solution on the substrate, a second step of statically developing the substrate in the puddle state, and a cleaning solution are supplied to the substrate after the static development. And a third step of cleaning the substrate, and the control of the zeta potential on the surface of the substrate may be performed over the first to third steps. The insolubilized substance of the resist film begins to be generated when the developing solution is supplied to the substrate and remains on the substrate until the substrate is cleaned. Therefore, like the developing treatment method, the insolubilized substance is spread from the first step to the third step. By controlling the electric potential of the substrate surface, it is possible to more reliably prevent the insoluble matter from adhering to the substrate surface.

According to a fourth aspect of the present invention, there is provided a developing method in which a developing solution is supplied onto the resist film formed on the surface of the substrate to develop the substrate, which is floating in the developing solution. There is provided a development processing method characterized in that a charging member charged with a polarity different from the zeta potential of the insoluble matter is brought into contact with the developing solution.

As in the present invention, the charging member charged with the opposite polarity to the insoluble matter is brought into contact with the developing solution,
The insoluble matter in the developer is adsorbed by the charging member, and the insoluble matter can be recovered. This can prevent the insoluble matter from adhering to the substrate surface. In this case, the charging member may be moved so as to be positively attracted.

This developing process includes a first step of piling a developing solution on the substrate and a second step of statically developing the substrate in the puddle state. The contact with the liquid may be performed during the second step. In this way, by contacting the charging member at the time of static development where most insoluble matter is generated, the insoluble matter can be more effectively collected by the charging member. Moreover, since the contact of the charging member is performed only in the second step, the supply of the developing solution in the first step, which is performed by a nozzle or the like, is performed without being blocked by the charging member.

In a development processing method in which a developing solution is supplied onto a resist film formed on the surface of a substrate to develop the substrate, the substrate is charged with the same polarity as the zeta potential of the insoluble matter floating in the developing solution. The charging member may be brought into contact with the developing solution on the substrate to move the charging member. As a result, the repelling force between the charging member and the insolubilized material allows the insolubilized material to be expelled from the substrate together with the developer. In such a case, it is more preferable to charge the substrate to the same polarity as the zeta potential of the insoluble matter. Further, it is preferable to charge the substrate so that the potential of the substrate is higher than that of the charging member.

Further, according to the present invention, there is provided a developing method in which a developing solution is supplied onto the resist film formed on the surface of the substrate to develop the substrate, and the developing solution is supplied to the substrate. A development processing method is provided, wherein a potential gradient is applied and the potential of the substrate is concentrically changed with time. This allows the insoluble matter to be driven from the center to the periphery.

Further, according to the present invention, there is provided a developing method in which a developing solution is supplied onto the resist film formed on the surface of the substrate to develop the substrate, wherein the temperature of the developing solution is higher than room temperature. For example, 25 ° C to 100 ° C, preferably 40
A development processing method is provided, which comprises supplying the resist film at a temperature of 80 ° C to 80 ° C. The temperature of the substrate may be higher than room temperature, for example 40 ° C. to 200 ° C., preferably 40 ° C. to 160 ° C., and the developing solution may be supplied onto the resist film. Of course, both may be used together. As a result, the resilience and solubility with the insolubilized material can be increased.

Furthermore, a first step of piling a developing solution on the substrate, a second step of statically developing the substrate in the puddle state, and a cleaning solution being supplied to the substrate after the static development. A third step of cleaning the substrate, and a cleaning solution for forming a liquid layer between the developing solution and the resist film surface between the second step and the third step, A development processing method characterized by supplying a liquid having a large specific gravity, such as HFE (hydrofluoroether), to the substrate can also be proposed. As a result, a layer of the liquid can be formed between the surface of the substrate and the developer in which the insoluble matter is floating, and this layer can prevent the insoluble matter in the developer from adhering to the substrate. it can.

According to the fourteenth aspect of the present invention, there is provided a developing treatment method of developing a substrate by supplying a developing solution onto a resist film formed on the surface of the substrate, wherein the ionic surfactant having a predetermined polarity is used. A developing treatment method is provided, which comprises adding an agent to the developing solution and causing the ionic surfactant to adhere to the insoluble matter suspended in the developing solution and the surface of the substrate.

By attaching an ionic surfactant so that the substrate surface and the insolubilized product have the same polarity, a reaction force is generated between the substrate surface and the insolubilized product, and the insolubilized product is deposited on the substrate surface. It can be prevented from adhering. As a result,
It is possible to reduce development defects caused by adhesion of insoluble matter on the substrate surface. Moreover, since insoluble matter does not adhere to the substrate surface,
The substrate cleaning time is shortened and the development processing time is shortened.

Instead of the ionic surfactant, a polymeric nonionic surfactant may be added to the developer. The polymeric nonionic surfactant is adsorbed on particles in the liquid, and repulsive force is generated in the adsorbed and overlapped polymer layers. As a result, the polymeric nonionic surfactant is Improves dispersion stability of the particles inside. The present invention utilizes this action of dispersion stability to adsorb a nonionic surfactant on the insolubilized material in the developer and the substrate surface to form a film on the insolubilized material and the substrate surface to form the insoluble material. Adhesion with the substrate surface can be prevented.

In the developing process, a first step of piling a developing solution on the substrate, a second step of statically developing the substrate in the puddle state, and a cleaning solution are supplied to the substrate after the static development. And a third step of cleaning the substrate, and the addition of the surfactant may be performed at the time of the first step. It should be noted that the first step includes immediately before the start of the first step and immediately after the end of the first step. In such a development processing method, since the surfactant is added to the developing solution in the first step in which insoluble matter starts to be generated, it is possible to prevent the insoluble matter from adhering to the substrate surface until the substrate is washed thereafter. Therefore, the adhesion of insoluble matter to the substrate surface can be prevented more reliably.

The addition of the surfactant may be performed during the third step as well as during the first step. In the third step, since the cleaning liquid is supplied onto the substrate, the concentration of the temporary surfactant decreases. According to this invention, the third
Since the surfactant is added again at the step of, and the surfactant is replenished, it is possible to more reliably prevent the insoluble matter remaining on the substrate from adhering to the substrate surface.

Further, the addition of the above-mentioned surfactant is carried out according to the above third step.
It may be performed only in the step of. When a surfactant is added to the developer, the quality of the developer slightly changes. Since the addition of the surfactant is not performed during the static development as in the present invention but is performed during the cleaning, the influence of the addition of the surfactant on the static development is eliminated, and the adhesion of the insoluble matter to the substrate surface can be suppressed. .

The resist solution may be mixed with an ionic surfactant having a predetermined polarity and applied on the surface of the substrate. Further, an ionic surfactant having a predetermined polarity may be supplied to the surface of the resist film before supplying the developing solution.

According to a twenty-first aspect of the present invention, there is provided a developing processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein the surface of the substrate has a zeta potential of a predetermined polarity. There is provided a development processing apparatus including a charging unit that charges the surface of the development processing apparatus. According to this invention,
The zeta potential on the surface of the substrate can be charged to a predetermined potential having the same polarity as the zeta potential of the insoluble substance in the developing solution by the charging means. Therefore, it is possible to prevent the insoluble matter from adhering to the substrate surface by causing an electric reaction force between the insoluble matter and the substrate surface. As a result, it is possible to reduce the development defects of the substrate due to the adhesion of the insoluble matter. Further, since the insoluble matter does not adhere to the surface of the substrate, the time of the cleaning process performed after the static development of the substrate can be shortened, and the total developing process time can be shortened.

The charging means comprises a conductive electrode plate and voltage applying means for applying a voltage of a predetermined polarity to the electrode plate, the electrode plate being attached to a holding member for holding a substrate, The substrate may be held by the holding member with the electrode plate interposed. In this case, when the substrate is held by the holding member, the zeta potential on the substrate surface can be controlled via the electrode plate.

Further, the voltage applying means may include a control unit for controlling the voltage applied to the electrode plate.
In this case, by controlling the voltage applied to the electrode plate, the zeta potential of the substrate surface in contact with the electrode plate can be freely controlled. Therefore, the data potential on the substrate surface can be controlled to a potential having the same polarity as the zeta potential of the insolubilized material and having a reaction force so that the insolubilized material does not adhere to the substrate surface.

According to the twenty-fourth aspect of the present invention, there is provided a developing processing apparatus for supplying a developing solution onto the resist film formed on the surface of the substrate to perform the developing process on the substrate, wherein a predetermined polarity is provided around the substrate. A development processing apparatus is provided, which is provided with an ion atmosphere supply unit that supplies the atmosphere containing the ions. According to the present invention, the atmosphere around the substrate can be replaced with an ionic atmosphere having a predetermined polarity. The ion atmosphere charges the surface of the substrate to the predetermined polarity. Therefore, the surface of the substrate can be charged with the same polarity as the zeta potential of the insoluble substance in the developer, and the insoluble substance can be prevented from adhering to the surface of the substrate.

According to a twenty-fifth aspect of the present invention, there is provided a developing processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, the charging member being capable of being charged to a predetermined polarity. And a charging member carrying means for carrying the charging member to bring it into contact with the developing solution on the substrate. According to the present invention, the charging member can be charged with a polarity different from the zeta potential of the insoluble matter floating in the developing solution, and the charging member can be brought into contact with the developing solution. By doing so, the insoluble matter floating in the developing solution is attracted to the charging member and collected. As a result, insoluble matter is prevented from adhering to the substrate surface. The charging member may have the same shape as the substrate so that the insoluble matter can be collected from the entire surface of the substrate.

According to a twenty-seventh aspect of the present invention, there is provided a developing treatment apparatus for performing a developing treatment on a substrate by supplying a developing solution onto a resist film formed on a surface of the substrate, wherein the substrate has an ionic property of a predetermined polarity. There is provided a development processing apparatus including a surfactant supply unit for supplying a surfactant.
According to a twenty-eighth aspect of the present invention, there is provided a development processing device for supplying a developing solution onto a resist film formed on a surface of a substrate to perform development processing on the substrate, the interface supplying a nonionic surfactant onto the substrate. There is provided a development processing apparatus including an activator supply unit. In claim 27, since an ionic surfactant having a predetermined polarity can be supplied into the developer and the ionic surfactant can be attached to the surface of the substrate and the insoluble matter in the developer, the same polar ion The reaction force can prevent the insoluble matter from adhering to the substrate surface. Also,
According to claim 28, the polymeric nonionic surfactant is adsorbed on the insolubilized product and the surface of the substrate to form a film on the surface of the insolubilized product and the surface of the substrate. The action of the dispersion stability of the agent prevents the insoluble matter from adhering to the substrate surface.

The development processing apparatus of the present invention is a development processing apparatus for supplying a developing solution onto a resist film formed on the surface of a substrate to develop the substrate, wherein the developing solution has a predetermined polarity. It is also possible to propose a development processing device, which is equipped with a charging means for charging the zeta potential. In such a case, the charging unit may include a device that applies a voltage to a pipe that supplies the developing solution. In this way, the developer itself may be charged.

Furthermore, there is also proposed a development processing apparatus having a charging member that is charged to the same polarity as the insoluble matter in the developing solution accumulated on the resist film, and a moving member that moves the charging member on the substrate. it can. This allows the charging member to be charged with the same or different polarity as the zeta potential of the insolubilized material and to be moved in contact with the developer on the substrate. In such a case, the charging member may be attached to a nozzle that supplies the developing solution onto the substrate.

Furthermore, a developing treatment apparatus for supplying a developing solution onto the resist film formed on the surface of the substrate to perform the developing treatment of the substrate, which is provided concentrically on the upper surface of the placing table on which the substrate is placed. It is also possible to propose a development processing apparatus having a plurality of electrodes, a power source for applying a voltage to each of the electrodes, and a control unit for changing the potential of each electrode with time. According to such an apparatus, a potential gradient can be applied to the substrate to which the developing solution is supplied, and the potential of the substrate can be changed concentrically with time. Can be driven away.

Furthermore, a developing treatment apparatus for supplying a developing solution onto the resist film formed on the surface of the substrate to perform the developing treatment of the substrate, characterized by comprising a heating device for heating the substrate, A development processor can also be proposed.

According to another aspect of the present invention, a resist solution is applied to the surface of the substrate to form a resist film, and a developing solution is supplied onto the formed resist film to develop the substrate. In the processing method, when the resist film has conductivity, a voltage is applied to the resist film so that the resist film has a potential of the same polarity as the insoluble matter in the developing solution at least during the developing process. We can propose a development processing method characterized by maintaining

As an apparatus for carrying out such a method, for example, a development processing apparatus having a mounting table for clamping and holding the substrate and a device for applying a voltage to the resist film of the substrate on the mounting table is described. I can propose.

By charging the resist film itself to the same polarity as the insolubilized material in this way, it is possible to suppress the insolubilized material floating in the developing solution from adhering to the substrate or the resist film due to repulsion.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below. FIG. 1 is a plan view showing an outline of the configuration of a coating and developing treatment system 1 having a developing treatment apparatus for carrying out the developing treatment method according to the present embodiment.
Is a front view of the coating and developing treatment system 1, and FIG.
It is a rear view of the coating and developing treatment system 1.

As shown in FIG. 1, the coating / developing processing system 1 carries in / out 25 wafers W from / into the coating / developing processing system 1 in a cassette unit from the outside or carries the wafer W into / from the cassette C, for example. A cassette station 2 for ejecting, a processing station 3 in which various processing devices for performing predetermined processing in a single-wafer type in a coating and developing processing process are arranged in multiple stages, and the processing station 3 is provided adjacent to the processing station 3. It has a configuration in which an interface section 4 for transferring the wafer W to and from an exposure apparatus (not shown) is integrally connected.

In the cassette station 2, a plurality of cassettes C can be placed in a line in the X direction (vertical direction in FIG. 1) at a predetermined position on the cassette placing table 5 serving as a placing portion. Then, this cassette arrangement direction (X direction) and the wafer arrangement direction of the wafers W accommodated in the cassette C (Z
Direction; vertical direction), a wafer transfer body 7 is provided so as to be movable along a transfer path 8 so that each cassette C can be selectively accessed.

The wafer carrier 7 has an alignment function for aligning the wafer W. The wafer carrier 7 is also configured to be accessible to the extension device 32 belonging to the third processing device group G3 on the processing station 3 side as described later.

The processing station 3 is provided with a main carrier unit 13 at the center thereof, and various processing units are arranged in multiple stages around the main carrier unit 13 to form a processing unit group. In this coating and developing treatment system 1, four processing device groups G1, G2, G3 and G4 are arranged, and the first and second processing device groups G1 and G2 are arranged on the front side of the coating and developing treatment system 1. The third processing unit group G3 is
The fourth processing unit group G4 is arranged adjacent to the cassette station 2, and the fourth processing unit group G4 is arranged adjacent to the interface unit 4. Further, as an option, a fifth processing unit group G5 indicated by a broken line can be separately arranged on the back side. The main transfer device 13 includes the processing device groups G1, G2, G3,
The wafer W can be loaded / unloaded into / from various processing devices, which will be described later, arranged in G4 and G5. The number and arrangement of the processing device groups differ depending on the type of processing performed on the wafer W, and the number of processing device groups can be arbitrarily selected as long as it is one or more.

In the first processing unit group G1, for example, as shown in FIG. 2, a resist coating device 17 for coating a resist liquid on the wafer W to form a resist film on the wafer W, and the development according to the present embodiment. The processing devices 18 are arranged in two stages in order from the bottom. Similarly, in the second processing device group G2, the resist coating device 19 and the developing processing device 20 are arranged in two stages in order from the bottom.

In the third processing unit group G3, for example, as shown in FIG. 3, a cooling unit 30 for cooling the wafer W,
An adhesion device 31 for enhancing the fixability of the resist liquid and the wafer W, an extension device 32 for transferring the wafer W, pre-baking devices 33, 34 for evaporating the solvent in the resist liquid, and a post-development processing device. Post-baking devices 35 for performing heat treatment are stacked in order from the bottom, for example, in six stages.

In the fourth processing unit group G4, for example, a cooling unit 40, an extension / cooling unit 41 for naturally cooling the mounted wafer W, an extension unit 42, a cooling unit 43, and a post-exposure baking for heating after exposure are performed. The devices 44 and 45 and the post-baking device 46 are stacked in order from the bottom, for example, in seven stages.

In the central part of the interface section 4, FIG.
For example, a wafer carrier 50 is provided as shown in FIG. The wafer carrier 50 is configured to be freely movable in the X direction (vertical direction in FIG. 1), the Z direction (vertical direction) and the θ direction (rotational direction around the Z axis). , The extension / cooling device 41, the extension device 42, the peripheral exposure device 51, and an exposure device (not shown) belonging to the fourth processing device group G4 can be accessed to transfer the wafer W to each of them. There is.

Next, the structure of the above-described developing processing device 18 will be described in detail. As shown in FIGS. 4 and 5, a spin chuck 60 as a holding member for adsorbing and holding the wafer W is provided in the casing 18 a of the development processing apparatus 18. A thin disk-shaped electrode plate 61 is attached to the upper surface of the spin chuck 60 as shown in FIG. As a material of the electrode plate 61, a conductor such as iron or copper is used. The upper surface of the electrode plate 61 is formed horizontally, and the electrode plate 61 is provided with a suction port 62. The spin chuck 60 sucks the wafer W onto the electrode plate 61 by suction from the suction port 62. The wafer W can be held horizontally. For example, on the lower surface of the electrode plate 61, a DC power source 64
A conductive wire 63 connected to is attached to the electrode plate 61 so that a voltage can be applied to the electrode plate 61. That is, a DC voltage can be applied to the electrode plate 61 to charge the electrode plate 61. The voltage of the DC power supply 64 and its polarity can be controlled by the controller 65, and the electrode plate 61 can be charged to a predetermined potential with a predetermined polarity. As a result, electrons in the wafer W adsorbed on the electrode plate 61 can be induced, and the zeta potential on the surface of the wafer W can be controlled to a predetermined potential with a predetermined polarity. In addition, the charging means in the present embodiment includes an electrode plate 61, a conductor wire 63,
It is composed of a DC power source 64 and a control unit 65. Further, the voltage adding means in the present embodiment is the DC power supply 64 and the control unit 65.

For example, as shown in FIG. 4, a drive mechanism 65 for driving the spin chuck 60 is provided below the spin chuck 60. The drive mechanism 65 includes a rotation drive unit (not shown) including a motor for rotating the spin chuck 60 at a predetermined rotation speed, the spin chuck 6 and the like.
A lifting drive unit (not shown) having a motor, a cylinder or the like for moving 0 up and down is provided. The elevating mechanism of the spin chuck 60 is for transferring the wafer W to and from the main carrier 13.

Outside the spin chuck 60, an annular cup 70 having an open upper surface is provided so as to surround the spin chuck 60. The cup 70 receives the developer and the like scattered from the wafer W which is held and rotated by the spin chuck 60 and prevents contamination of peripheral devices. At the bottom of the cup 70, a drain pipe 71 for draining the developer and the like scattered from the wafer W and the cup 7 are provided.
An exhaust pipe 72 for exhausting the atmosphere inside 0 is connected.

On the outside of the cup 70, a square out cup 75 having an open upper surface is provided so as to surround the cup 70, and the developing solution from the wafer W which cannot be received by the cup 70. It can catch the developer and prevent the developer from scattering. In addition, in the out cup 75,
A drive mechanism (not shown) that allows the out cup 75 to move up and down is provided so that, for example, when the wafer W is cleaned, it rises and the scattered cleaning liquid or the like can be collected more reliably.

As shown in FIG. 5, on the outside of the out cup 75, for example, on the outside in the negative direction of the M direction (left side in FIG. 5),
A standby unit T is installed, and a developer supply nozzle 80 for supplying a developer to the wafer W can stand by in the standby unit T.

The developing solution supply nozzle 80 has an elongated shape as shown in FIG. 7, and its length L is at least larger than the diameter of the wafer W. A pipe 81 communicating with a developer supply source (not shown) is connected to the upper portion of the developer supply nozzle 80. Below the developing solution supply nozzle 80, a plurality of developing solution supply ports 82 are provided in a line in the longitudinal direction. Further, as shown in FIG. 8, inside the developing solution supply nozzle 80, a liquid reservoir portion 83 communicating with each of the developing solution supply ports 82 and a pipe 81 is formed long in the longitudinal direction. The developing solution that has flowed into the supply nozzle 80 is temporarily stored, and the developing solution can be simultaneously discharged from the respective developing solution supply ports 82 at the same flow rate and the same pressure.

The developer supply nozzle 80 is held by an arm 85 as shown in FIG. 5, and this arm 85 is moved on a rail 86 laid in the M direction (left and right direction in FIG. 5) by a moving mechanism (not shown). You are free. Rail 86 is
It extends from the standby portion T to the outside of the out cup 75 on the positive side in the M direction, and the developer supply nozzle 80 can move at least from the standby portion T to the outside of the cup 70 on the positive side in the M direction. The developing solution supply nozzle 80 is held by the arm 85 so that the longitudinal direction is perpendicular to the M direction.
By moving the developing solution supply nozzle 80 on the wafer W while discharging the developing solution from each developing solution supply port 82 of the developing solution supply nozzle 80, the developing solution can be supplied to the entire surface of the wafer W. The arm 85 is equipped with an elevating mechanism (not shown). The developing solution supply nozzle 80 is moved up and down as necessary to adjust the distance between the standby section T and the cleaning tank 87, which will be described later, and the distance to the wafer W. And so on.

The standby portion T is provided with a cleaning tank 87 for cleaning the developing solution supply nozzle 80. This washing tank 87
Has a concave cross section so as to accommodate the elongated developer supply nozzle 80, and a predetermined solvent for cleaning the developer adhered to the developer supply nozzle 80 is stored in the cleaning tank 87. Can be stored.

A standby portion U of the cleaning liquid supply nozzle 90 for supplying the cleaning liquid to the wafer W is provided outside the positive side of the out cup 75 in the M direction (right side in FIG. 5).
The cleaning liquid supply nozzle 90 is held by a rinse arm 91, and this rinse arm 91 is, for example, the arm 8 described above.
It is possible to move on the same rail 86 as No. 5. The cleaning liquid supply nozzle 90 is held by the rinse arm 91 so that the cleaning liquid can be supplied to the central portion of the wafer W when the cleaning liquid supply nozzle 90 moves onto the wafer W in the cup 70. Also, in the standby unit U,
For example, a cleaning tank 92 for the cleaning liquid supply nozzle 90 is provided, and for example, the cleaning liquid supply nozzle 90 can be immersed in the cleaning tank 92 in which a solvent is stored to remove impurities attached to the cleaning liquid supply nozzle 90.

The side surface of the casing 18a has a transfer port 1 for loading / unloading the wafer W into / from the development processing apparatus 18.
00 is provided, and the transfer port 100 has a shutter 101
Can be opened and closed freely.

Next, the development processing method carried out by the development processing apparatus 18 having the above-mentioned structure will be described together with the photolithography process carried out in the coating and developing processing system 1.

First, one unprocessed wafer W is taken out from the cassette C by the wafer transfer body 7 and transferred to the extension device 32 belonging to the third processing device group G3.
Next, the wafer W is carried into the adhesion device 31 by the main carrier 13 and coated with, for example, HMDS, which improves the adhesion of the resist solution onto the wafer W. Next, the wafer W is transferred to the cooling device 30, cooled to a predetermined temperature, and then transferred to the resist coating device 17. In the resist coating process 17, a positive resist solution such as a photosensitive resin is supplied to the wafer W, and a resist film is formed on the wafer W. After that, the wafer W is sequentially transferred by the main transfer device 13 to the pre-baking device 33 and the extension / cooling device 41, and further transferred to the peripheral exposure device 51 by the wafer transfer body 50, and subjected to predetermined processing in each device. Next, the wafer W is transferred to an exposure device (not shown), and a predetermined circuit pattern is exposed on the wafer W by, for example, irradiation with ultraviolet rays. At this time, the exposed portion of the resist film becomes soluble in the alkaline solution.
The wafer W after the exposure processing is transferred to the extension device 42 by the wafer transfer body 50, and then the wafer W is subjected to predetermined processing by the post-exposure baking device 44 and the cooling device 43, and then transferred to the development processing device 18. It is conveyed and developed.

The wafer W which has undergone the development processing in the development processing apparatus 18 is sequentially transferred to the post-baking apparatus 46 and the cooling apparatus 30 and subjected to a predetermined processing in each apparatus, and then the cassette C via the extension apparatus 32. Then, the series of photolithography steps are completed.

Next, the developing process performed by the above-described developing device 18 will be described in detail. FIG. 9 shows a flowchart of this developing process. In the present embodiment, a strong alkaline aqueous solution such as TMAH (N (CH ₃ ) ₄ OH) having a pH of about 13 is used as the developing solution.

First, the wafer W is loaded into the casing 18a from the transfer port 100 by the main transfer device 13 and held by suction on the spin chuck 60 (step S1). When the wafer W is suction-held, the developer supply nozzle 80 of the standby portion T moves to the start position S inside the cup 70 and near the end of the wafer W on the negative side in the M direction (step S2). . Next, with the developer supply nozzle 80 stopped at the start position S, the discharge of the developer is started, and so-called pre-dispensing is performed until the discharge state of the developer from each developer supply port 82 becomes stable (step S
3).

Before proceeding to the next step S4, the DC voltage 63 applies a cathode voltage to the electrode plate 61 on the spin chuck 60, and the electrode plate 61 is charged with negative charges as shown in FIG. To be done. As a result, the electrode plate 61
The lower surface of the wafer W which is in contact with is charged to a positive charge by electrostatic induction, and the upper surface of the wafer W is charged to a negative charge. Therefore, the zeta potential on the surface of the wafer W becomes negative. Further, the lower portion of the resist film R having the wafer W as a base is positively charged, and the upper portion thereof is negatively charged. The control unit 65 uses the DC power source 6
The voltage of 3 is adjusted to control the zeta potential of the wafer surface to a predetermined set potential, for example, about −70 mV. The polarity of the voltage applied to the electrode plate 61 is determined to be the same polarity as the zeta potential of the insolubilized product Y of the resist film R due to the developing solution described later. The polarity of the zeta potential of this insolubilized substance is obtained in advance by experiments,
The zeta potential of the insoluble material Y in the present embodiment is, for example, −20 mV in a developing solution having a pH of 13. As the set potential on the surface of the wafer W, for example, an optimum potential for preventing insoluble matter from adhering to the wafer surface is obtained in advance for each type of resist film and type of developing solution by, for example, an experiment.
For example, it is stored in the control unit 65. It is also possible to measure the amount of insoluble matter deposited on the surface of the wafer W after the development processing and change the set potential based on the measured value.

After the discharge state from the developing solution supply nozzle 80 is stabilized and the wafer W is charged, the developing solution discharge nozzle 80
Moves to the M direction positive direction side while discharging the developing solution, passes over the wafer W, and moves to the end position E near the end of the wafer W on the M direction positive direction side. As a result, a predetermined amount of the developer puddle is formed on the wafer W (step S
4) Subsequently, the wafer W is subjected to static development for a predetermined time (step S5). By supplying this developer,
As shown in FIG. 1, most of the resist film R in the exposed portion is dissolved in the developing solution, and the other part is deposited as insoluble matter Y in the developing solution and floats. The insoluble material Y has a negative zeta potential as described above, and a reaction force is generated between the surface of the wafer W which is also negatively charged and the insoluble resist film R. Therefore, the insoluble material Y does not adhere to the surface of the wafer W or the resist film R on the insoluble portion. The developing solution supply nozzle 80 stopped at the end position E stops the discharging of the developing solution and is returned to the standby section T. Note that in the present embodiment, the first
This step corresponds to step S4, and the second step corresponds to step S5.

Then, when the static development for a predetermined time is completed,
The cleaning liquid supply nozzle 90 moves to above the central portion of the wafer W, and ejects the cleaning liquid, for example, pure water, onto the wafer W (step S6). For example, the wafer W is rotated simultaneously with the supply of the pure water, and the developer on the wafer W is replaced with pure water. At this time, the pH of the developing solution on the wafer W drops sharply and approaches pH 7 which is neutral. At this time, the zeta potential of the insolubilized material Y, which was -20 mV, drops to, for example, -60 mV, the absolute value of the zeta potential increases, and the tendency of the insolubilized material Y to adhere to the surface of the wafer W is higher than that during static development. Weaken. In addition, in the present embodiment, the third step corresponds to step S6.

Even after the developing solution is replaced with pure water, the wafer W
Is continuously rotated, and the insoluble material Y on the wafer W is completely removed (step S7). Thereafter, the discharge of pure water is stopped, the wafer W is rotated at a high speed, and the wafer W is shaken off and dried (step S8). For example, when the drying process of the wafer W is finished, the application of the voltage to the electrode plate 61 is finished, and, for example, the electric charges charged on the wafer W are grounded.
Then, the wafer W is transferred from the spin chuck 60 to the main transfer device 13, and the wafer W is carried out of the development processing device 18 (step S9), and a series of development processing is completed.

According to the above-described embodiment, the electrode plate 61 is provided on the spin chuck 60 for holding the wafer W so that the zeta potential on the surface of the wafer W has the same negative polarity as that of the insoluble material Y in the developing solution. Therefore, a reaction force always acts between the insoluble material Y and the surface of the wafer W. Moreover, since the absolute value of the zeta potential on the surface of the wafer W is set to be sufficiently large, even if the zeta potential of the insoluble matter Y fluctuates, a strong reaction force is maintained between the insoluble matter Y and the surface of the wafer W. Therefore, insoluble matter Y
Can be prevented from adhering to the surface of the wafer W.

Further, the zeta potential on the surface of the wafer W is controlled from the step S4 before the insoluble matter Y is generated in the developing solution to the step S8 at which the insoluble matter Y on the wafer W is removed. The adhesion of insoluble matter Y can be completely prevented.

In the developing method described in the above embodiment, the wafer surface which is the base of the resist film R is charged with a predetermined polarity, but the developer supplied onto the wafer W has a predetermined polarity. You may make it contact the charged charging member.

FIG. 12 shows an example of the development processing apparatus 110 for realizing such a development processing method. For example, the charging member 111 is on standby in the standby portion K on the positive side in the M direction of the out cup 75. The charging member 111 is formed, for example, in a disk shape having the same shape as the wafer W, and the material thereof is, for example, a metal having excellent conductivity such as iron or copper. On the upper surface of the charging member 111, for example, a conducting wire 113 connected to the DC power supply 112 is attached, so that the control unit 114 of the DC power supply 112 can adjust the polarity of the charge charged on the charging member 111 and the charge amount of the charge. It has become.

The charging member 111 is held by a holding arm 115 serving as a charging member carrying means. Holding arm 1
15 is movable in the M direction on the rail 116 laid from the standby portion K to the vicinity of the cup 70, and the charging member 11 is provided.
1 can be moved onto the wafer W in the cup 70. Further, as shown in FIG. 13, the holding arm 115 is provided with a cylinder 117 which is a lifting mechanism and can move up and down. Therefore, the charging member 111 can move from the standby portion K onto the wafer W and then descend to approach the wafer W so as to match the surface of the wafer W. The standby unit K is provided with, for example, a cleaning tank 118 for cleaning the charging member 111 by immersing the charging member 111 in a predetermined solution. The cleaning tank 118 is, for example, the charging member 11
1 has the same shape, for example, a circular shape when seen from a plane. The other members of the development processing device 110 are the same as those of the development processing device 18, and thus the description thereof is omitted.

In the development processing in the development processing apparatus 110, for example, as shown in FIG. 14, the charging member 111, which is positively charged, is transferred from the standby portion K to the wafer W after completion of the developing solution piling step S4. The wafer W is conveyed to the opposite position and is brought into contact with the developer on the wafer W. In this state, when the static development for a predetermined time in step S5 is performed,
As shown in FIG. 15, the insoluble material Y having a negative zeta potential deposited from the resist film R is attracted to the charging member 111 and adheres to the charging member 111. When the static development is completed, the charging member 111 that has collected a large amount of insoluble matter Y is withdrawn from the wafer W and returned to the standby section K. The charging member 111 returned to the standby portion K is immersed in the cleaning tank 118, and the insoluble material Y is washed off.

According to this embodiment, the charging member 111 charged with a sign different from that of the insoluble matter Y is brought into contact with the developing solution on the wafer W, so that the insoluble matter Y in the developing solution is charged by the charging member 111. Then, the charging member 111 can collect the insoluble matter Y. Therefore, insoluble matter Y
Can be prevented from adhering to the surface of the wafer W. Further, the holding arm 115 may be moved to positively move the charging member 111 to promote the insoluble matter Y in the developing solution to adhere to the charging member 111.

The shape of the charging member 111 may be a shape other than a circular shape, such as a square shape. Further, instead of the charging member 111, an ionic atmosphere having the same polarity as that of the insoluble matter Y is supplied to the periphery of the surface of the wafer W to charge the surface of the wafer W to a predetermined polarity and the insoluble matter Y adheres to the wafer W. May be prevented. In such a case, for example, FIG.
As shown in FIG.
An ionizer 121 is provided as an ion atmosphere supply unit that supplies an ion atmosphere containing ions of a predetermined polarity in 20a. Then, at least between the generation of the insoluble matter Y and the removal of the insoluble matter Y, the casing 120
The inside of a is maintained in an anion atmosphere. Due to this ionic atmosphere, the surface of the wafer W is negatively charged and the negative insoluble matter Y
Can be prevented from adhering to the surface of the wafer W. It should be noted that the ionizer 121 may be installed on the upstream side of the air flow in the development processing apparatus 120 so as to more efficiently supply the wafer W with the anion atmosphere. Also, the ionizer 12
1 may use corona discharge or soft X-rays. Further, although such an ionizer is mainly a means for charging a gas, a means for charging a steam mist or the like may be used.

Instead of bringing the charging member 111 into contact with the developing solution, an ionic surfactant having a predetermined polarity is added to the developing solution to prevent the insoluble matter Y from adhering to the surface of the wafer W. Good.

FIG. 17 shows an example of the development processing apparatus 130 for realizing the development processing in such a case. For example, in the development processing apparatus 130, a surfactant supply unit for supplying an ionic surfactant is provided. Surfactant supply nozzle 1
31 is provided. This surfactant supply nozzle 13
No. 1 is held by, for example, a nozzle arm 132, and this nozzle arm 132 has a rail 133 extending in the M direction.
It is provided so that it can move freely. The rail 133 is laid, for example, on the opposite side of the rail 86 of the developer supply nozzle 80 via the cup 70, and the surfactant supply nozzle 1
The reference numeral 31 can move to a position above the center of the wafer W on the spin chuck 60.

In the development processing in the development processing apparatus 130, the ionic surfactant is supplied to the wafer W immediately after the developing solution is filled in step S4 as shown in FIG. As shown in FIG. 19, the surface active agent supplied onto the wafer W is removed from the surface of the wafer W and the resist film R.
It adheres to the surface and the surface of the insoluble matter Y. As a result, the same polarity,
For example, the surface of the wafer W covered with anions, the insoluble material Y, and the like repel each other, and the insoluble material Y is prevented from adhering to the wafer surface and the like. Further, in this case, since the insoluble matter Y is supplied with the surfactant when it starts to be generated, it is possible to more reliably prevent the insoluble matter Y from adhering to the wafer surface or the like. The surfactant may be supplied immediately before step S4, or may be supplied at step S4.

Also, an ionic surfactant may be supplied onto the wafer W during the pure water supply in step S6. Anions that are reduced by the supply of pure water can be replenished on the surface of the wafer W to prevent the insoluble matter Y from adhering to the surface of the wafer W during cleaning. The ionic surfactant may be supplied only during the pure water supply in step S6. In this case, the property of the developer during the static development in step S5 is excellent in that it is not affected by the surfactant at all.

Further, the surfactant supply nozzle 131 may have the same structure as that of the developer supply nozzle 80, and the surfactant may be supplied to the entire surface of the wafer W by scanning.

Further, instead of the ionic surfactant, a high molecular nonionic surfactant may be supplied onto the wafer W. The polymeric nonionic activator has a property of adsorbing to particles in the liquid, and repulsive force is generated in the adsorbed and overlapped polymer layers. As a result, the polymeric nonionic activator is It has the effect of improving dispersion stability. This is considered to be due to the osmotic pressure effect or volume limiting effect of the polymeric nonionic surfactant. Therefore, when the nonionic surfactant is supplied into the developer on the wafer W, the nonionic surfactant is adsorbed on the insolubilized product Y, the surface of the wafer W and the surface of the resist film R as shown in FIG. However, the dispersion stabilizing action of these can prevent the insoluble matter Y from adhering to the surface of the wafer W or the like. As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. are used.

As shown in FIG. 21, a supply pipe 141 connecting the surfactant supply nozzle 131 and the surfactant buffer tank 140 may be provided with a concentration adjusting device 142 capable of adjusting the concentration of the surfactant. Good. The concentration of the surfactant supplied on the wafer W is changed according to the type of resist film, the type of developing solution, and the like. For example, when the absolute value of the zeta potential of the insolubilized material Y is relatively small and it is easy to aggregate, the concentration of the surfactant is set high. By doing this,
A larger amount of the surfactant is adsorbed on the surface of the insoluble material Y or the wafer W, and the reaction force between the surface of the insoluble material Y and the surface of the wafer W is increased, and the adhesion of the insoluble material Y can be appropriately prevented. In addition,
For each type of resist film and developer, the optimum concentration of the surfactant that reduces the amount of the insolubilized material Y deposited is obtained in advance by experiments or the like, and the optimum concentration is stored in the concentration adjusting device 142 or the like. The concentration of the agent may be adjusted to its optimum concentration. Further, the concentration adjusting device 142 may be one that adjusts the concentration by, for example, mixing a surfactant passing through the supply pipe 141 with a predetermined amount of solvent according to the set concentration.

Further, the surfactant may be supplied onto the wafer W from the above-mentioned developing solution supply nozzle 80.
In this case, for example, as shown in FIG. 22, a branch pipe 153 communicating with the surfactant buffer tank 152 is attached to a supply pipe 151 that connects the developer supply nozzle 80 and the developer storage tank 150 to each other. 153 and supply pipe 1
You may make it provide the three-way valve 154 in the connection part with 51. The developer and the surfactant are selectively supplied to the developer supply nozzle 80 by the three-way valve 154, and the surfactant is discharged onto the wafer W at the predetermined timing as described above. Further, a surfactant may be added to the developing solution. In this case, a predetermined amount of the surfactant may be added to the developing solution in advance, and the developing solution may be supplied to the developing solution supply nozzle 80 while being fed. A surfactant may be added in the supply pipe 151.

In the above-described embodiment, the surfactant is mixed with the developer, or the surfactant is added when the developer is puddle on the wafer W. Before supplying the liquid onto the wafer W, a surfactant, vapor of the surfactant or mist may be supplied onto the wafer W. This method can also prevent the insoluble matter from adhering to the substrate.

The above-described surfactant is mixed in the resist solution in advance, and when the resist solution is applied to the wafer W in the resist application devices 17 and 19, the resist solution containing the surfactant is applied. May be. This method can also prevent the insoluble matter from adhering to the substrate.

By the way, conventionally, the temperature of the wafer W and the temperature of the developing solution supplied to the wafer W are room temperature, for example, 2
Although the developing process was performed while maintaining the temperature at around 3 ° C, the temperature of the developing solution was higher than room temperature, for example, 25 ° C to 80 ° C.
More preferably, the temperature is set to 40 ° C. to 60 ° C., or the temperature of the wafer W is set to 40 ° C. to 200 ° C., more preferably 40 ° C. to 160 ° C. It is possible to suppress the adhesion of the insolubilized product to the resist film. This is because, for example, when the repulsive force between the zeta potential of the insoluble material and the potential of the resist film is weak, the repulsive force can be increased by raising the temperature of the substrate or the developing solution. To raise the temperature of the developing solution, an appropriate heating device may be adopted.

As described above, the conventional development processing apparatus is
Since the substrate is processed at room temperature, there is no device for raising the temperature of the substrate inside the device. Therefore, in order to raise the temperature of the substrate proposed in the present invention and perform the developing process, for example, the apparatus shown in FIG. 23 can be proposed.

In the device example of FIG. 23, the casing 18
The lamp heating device 161 is provided on the ceiling portion of the inside of a. Thereby, for example, the temperature of the wafer W can be heated to a temperature higher than room temperature, for example, 40 ° C. to 60 ° C. to perform the developing process of the wafer W.

In order to raise the temperature of the developing solution supplied to the wafer W, a temperature adjusting mechanism conventionally used for the developing solution supply nozzle 80, for example, a temperature adjusting fluid is supplied to the nozzle to develop it. In the mechanism for adjusting the temperature of the liquid, it is preferable to raise the temperature of the fluid.

Next, an example using a charging member having the same polarity as the zeta potential of the insoluble material in the developing solution will be described. FIG. 24 shows a plan view of an example of such an apparatus.
A charging member 171 is mounted in parallel to the developing solution supply nozzle 80 via a bracket 172 in parallel with 0. The charging member 171 is set to have the same length as the developing solution supply nozzle 80, and the height position of the lower surface thereof is also set to be the same as that of the developing solution supply nozzle 80. Then, a voltage from a power source 173 is applied to the charging member 171. As a result, the charging member 171 can be charged with the same polarity as the zeta potential of the insoluble matter in the developing solution.

The charging member 171 thus charged to the same polarity as the zeta potential of the insoluble material is used as follows. That is, the wafer W
After the developing solution is deposited on the wafer W, as shown in FIGS. 25 and 26, the arm 85 is moved to scan the charging member 171 with the developing solution supply nozzle 80 on the wafer W. At this time, as shown in FIG. 26, the charging member 171 is attached to the wafer W.
The developer DL above is brought into contact.

As a result, the insoluble matter floating in the developing solution DL repels the charging member 171 and moves.
Then, by scanning the charging member 171, the insoluble matter moves in the developing solution DL and is expelled from the edge of the wafer W together with the developing solution DL. Therefore, in this apparatus example, the repulsion between the charging member 171 and the insoluble matter is used to expel a considerable number of the wafer W together with the developing solution DL. As a result, the insoluble matter is prevented from adhering to the resist film and the wafer W.

As described above, the charging member 171 is
If the zeta potential of the insoluble matter in the developer is charged and moved to the same polarity, the wafer is also preferably charged to the same polarity as the zeta potential of the insoluble matter. This is because the insoluble matter and the wafer also repel each other and the insoluble matter can be prevented from approaching the wafer side. Therefore, it is possible to more effectively prevent the insoluble matter from adhering to the resist film and the wafer W. In order to charge the wafer W with the same polarity as the zeta potential of the insoluble matter, for example, the DC power supply 64 may be used. Furthermore, when charging the charging member 171 and the wafer W to the same polarity, it is preferable to charge the wafer W so that the potential of the wafer W becomes higher than that of the charging member 171. This is because it is possible to further prevent the insoluble matter from approaching the wafer W side.

Besides, the example shown in FIG. 27 can be proposed. Figure 2
7 is a zone electrode 181, on the surface of the spin chuck 60,
An example in which 182 and 183 are arranged concentrically is shown.
The spin chuck 60 has the same size as the wafer W to be mounted. The zone electrodes 181, 182, 183 are arranged at a predetermined interval. Each zone electrode 181, 182
183 includes power sources 184, 185, 18 for applying a voltage.
6 is connected, and the control device 187 controls the application timing and the applied voltage value. The voltage can be applied in pulses. In the figure, CEN represents the center of the wafer W, and EDG represents the edge portion of the wafer W.

Such an apparatus is used as follows.
That is, as shown in FIG. 28, under the control of the control device 187, for example, a region corresponding to the zone electrode 183 located on the outermost periphery of the wafer W is charged to the positive side, and then the zone electrode 182 on the inner side is charged. The zone electrode 181 that is located in the center is charged with the area to the negative side.
The region corresponding to is charged to a stronger negative side and the wafer W is given a potential gradient. In this state, for example, by controlling the voltage application from the zone electrodes 182, 183,
The applied voltage value to each electrode is changed at every predetermined timing. For example, strong and weak voltages are alternately applied to the zone electrodes 182 and 183. At this time, the zone electrode 182,
The negative charge on the area corresponding to 183 is maintained.

Such zone electrodes 181, 182, 1
When the potential control with respect to each region of the wafer W is caused by the application control of 83, a wave due to the movement of the potential is generated as shown in FIG. 30, and as a result, the developer in the developer on the wafer W is negatively charged. The insoluble matter having the zeta potential is driven to the outer peripheral side of the wafer W by the wave.

After that, if the developing solution is shaken off from the outer periphery of the wafer W by rotating the spin chuck 60 or the like, it is possible to prevent the insoluble matter from adhering to the resist film of the wafer W.

A voltage may be applied to the developing solution supplied from the developing solution supply nozzle 80 before it is discharged from the developing solution supply nozzle 80. For example, as shown in FIG. 31, a pipe having a conductive material is used for a part of the supply pipe 191 connected to the developing solution supply nozzle 80, and an insulating member 192 is provided at both ends thereof.
Place 193. Then, a voltage is applied to the pipe 191 by the power supply 194. As a result, the developing solution DL is charged when passing through the pipe 191, and is directly supplied to the wafer from the developing solution supply nozzle 80.

Then, the developer DL is charged with the same polarity as the zeta potential of the insoluble matter, so that the wafer W
Even if an insoluble matter is generated in the developing solution supplied on the resist film at the stage of the developing treatment, it is possible to prevent the insoluble matter from adhering to the resist film due to the repulsion due to the same polarity.

When the resist film formed on the wafer has conductivity, by charging the resist film itself, the resist film of insoluble matter floating in the developing solution is repelled by the repulsion due to the same polarity. Can be suppressed.

FIG. 32 shows an example of a structure in which a voltage is applied to the resist film 201 on the wafer W in such a manner. The outer edge of the mounting table 202 such as a spin chuck for supporting the wafer W is A clamp 203 is attached. The clamp 203 directly clamps the end portion of the wafer W and holds the wafer W on the mounting table 202. The power supply 2 is connected to the clamp 203 itself or electrodes (not shown) provided in parallel with the clamp 203.
04, by applying a voltage, the resist film 20
It is possible to charge 1 to a potential of a predetermined polarity.

After the static development is completed by supplying the developing solution to the wafer W and before the cleaning, the developing solution on the wafer W has a specific gravity larger than that of the developing solution and is subjected to the development reaction. You may make it supply the liquid which does not affect, for example, HFE (hydrofluoro ether). For that purpose, for example, as shown in FIG. 33, a nozzle 211 for supplying the liquid may be provided in the development processing apparatus 18.

When such a liquid having a larger specific gravity than the developing solution is supplied into the developing solution, as shown in FIG. 34, the resist film R and the developing solution D in which the insolubilized material is floating are formed.
A layer 212 of the liquid can be formed between L and
This layer 212 can prevent the insoluble matter in the developer DL from adhering to the resist film R.

In the above embodiment, the present invention is applied to the developing processing method for the wafer W. However, the present invention is applied to the developing processing of substrates other than semiconductor wafers such as LCD substrates and mask reticle substrates for photomasks. It can also be applied in methods.

[0105]

According to the present invention, it is possible to prevent the insoluble matter floating in the developing solution from adhering to the surface of the substrate, so that the developing process can be optimized and the yield can be improved. In addition, since the cleaning time during the developing process can be shortened, the throughput of substrate processing can be improved.

[Brief description of drawings]

FIG. 1 is a plan view showing the outer appearance of a coating and developing treatment system having a developing treatment apparatus for carrying out the developing treatment method according to the present embodiment.

FIG. 2 is a front view of the coating and developing treatment system of FIG.

FIG. 3 is a rear view of the coating and developing treatment system of FIG.

FIG. 4 is an explanatory view of a vertical cross section of the development processing apparatus.

FIG. 5 is an explanatory view of a cross section of the development processing apparatus.

FIG. 6 is a perspective view of a spin chuck of the development processing apparatus.

FIG. 7 is a perspective view of a developing solution supply nozzle.

8 is a vertical cross-sectional view of the developer supply nozzle of FIG.

FIG. 9 is a flowchart of a developing process.

FIG. 10 is an explanatory view of a vertical cross section of a wafer showing a state of electric charges when the wafer is charged.

FIG. 11 is an explanatory diagram of a vertical cross section of a wafer showing a state of an insoluble matter of a developing solution.

FIG. 12 is an explanatory diagram of a cross section of a developing processing apparatus including a charging member.

FIG. 13 is an explanatory diagram showing a configuration of a holding arm.

FIG. 14 is a flowchart of a developing process using a charging member.

FIG. 15 is an explanatory view of a vertical cross section of a wafer showing a state of insoluble matter when a charging member is brought into contact with a developing solution.

FIG. 16 is an explanatory diagram of a vertical cross section showing a configuration of a development processing apparatus including an ionizer.

FIG. 17 is an explanatory diagram of a cross section showing a configuration of a development processing apparatus including a surfactant supply nozzle.

FIG. 18 is a flow chart of a developing process for supplying a surfactant.

FIG. 19 is an explanatory view of a vertical cross section of a wafer showing a state of the wafer when an ionic surfactant is added.

FIG. 20 is an explanatory diagram of a vertical cross section of a wafer showing a state of the wafer when a nonionic surfactant is added.

FIG. 21 is an explanatory diagram showing a configuration of a supply system of a surfactant supply nozzle.

FIG. 22 is an explanatory diagram showing a configuration of a supply system of another surfactant supply nozzle.

FIG. 23 is a side sectional view of a development processing apparatus having a device for heating a substrate.

FIG. 24 is a plan view of an apparatus in which a charging member is attached to a developing solution supply nozzle.

25 is a plan view showing how the charging member of FIG. 24 is scanned on the wafer together with the developing solution supply nozzle.

FIG. 26 is a side view showing a state in which the charging member of FIG. 24 is scanned on the wafer together with the developing solution supply nozzle.

FIG. 27 is a plan view of a spin chuck having zone electrodes.

FIG. 28 is an explanatory diagram showing a potential gradient of a substrate due to zone electrodes.

FIG. 29 is an explanatory diagram showing changes in potential due to control of zone electrodes.

FIG. 30 is an explanatory diagram showing waves caused by changes in potential with time.

FIG. 31 is an explanatory diagram showing a configuration for applying a voltage to the pipe of the developing solution supply nozzle.

FIG. 32 is an explanatory diagram showing a configuration for applying a voltage to a resist film on a wafer.

FIG. 33 is a side sectional view of a development processing apparatus having a nozzle that supplies a liquid having a specific gravity larger than that of a developing solution to a wafer.

FIG. 34 is an explanatory diagram showing a state after a liquid having a larger specific gravity than the developing solution is supplied to the developing solution on the resist film.

[Explanation of symbols]

1 Coating and developing system 18 Development Processing Equipment 60 spin chuck 61 electrode plate 63 DC power supply 65 Control unit 80 developer supply nozzle S start position E end position W wafer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H096 AA25 BA01 BA09 GA29                 4D075 BB65Z BB81Y CA47 DA08                       DB14 DC22 EA07 EA45 EA60                       EC35                 4F042 AA02 AA07 BA21 EB05 EB09                       EB18                 5F046 LA05 LA08 LA12

Claims (36)

[Claims] 1. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein the zeta potential of the surface of the substrate is suspended in the developing solution. The developing treatment method is characterized in that the developing treatment is carried out by controlling to a predetermined potential having the same polarity as the zeta potential of the insoluble matter. 2. The absolute value of the zeta potential of the substrate surface is 3
The development processing method according to claim 1, wherein the zeta potential on the surface of the substrate is controlled so as to be 0 mV or higher. 3. The developing treatment comprises a first step of piling a developing solution on a substrate, a second step of statically developing the substrate in the puddle state, and a cleaning solution for the substrate after the static development. And a third step of cleaning the substrate, wherein the control of the zeta potential on the surface of the substrate is performed over the first to third steps. Or 2
The development processing method according to any one of 1. 4. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, the method being different from a zeta potential of an insoluble matter floating in the developing solution. A development processing method, characterized in that a charging member charged in polarity is brought into contact with the developing solution. 5. The development processing method according to claim 4, wherein the charging member charged with the opposite polarity is moved while being in contact with the developing solution. 6. The developing process includes a first step of piling a developing solution on a substrate, and a second step of statically developing the substrate in the puddle state. The development processing method according to claim 4, wherein the contact with the developing solution is performed during the second step. 7. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, the method being the same as a zeta potential of an insoluble matter floating in the developing solution. A development processing method, wherein a charging member charged to a polarity is brought into contact with a developing solution on the substrate to move the charging member. 8. The development processing method according to claim 7, wherein the substrate is charged to have the same polarity as the zeta potential of the insoluble matter while at least the charging member is in contact with the developing solution. 9. The development processing method according to claim 8, wherein the substrate is charged so that the potential of the substrate is higher than that of the charging member. 10. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein a potential gradient is applied to the substrate supplied with the developing solution. A development processing method characterized in that the potential of the substrate is changed concentrically with time. 11. A development processing method for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein the temperature of the developing solution is set to a temperature higher than room temperature. A developing method, which is characterized by supplying. 12. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein the temperature of the substrate is higher than room temperature. A developing method comprising supplying a developing solution. 13. A development processing method for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, comprising: a first step of piling the developing solution on the substrate; A second step of statically developing the substrate in a liquid-filled state,
A third step of cleaning the substrate by supplying a cleaning solution to the substrate after the static development, and between the second step and the third step, the developing solution and the resist film surface are separated from each other. In the meantime, a developing treatment method, characterized in that a liquid having a larger specific gravity than the cleaning liquid for forming a liquid layer is supplied to the substrate. 14. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein an ionic surfactant having a predetermined polarity is added to the developing solution. Then, the insoluble matter floating in the developer and the ionic surfactant are adhered to the surface of the substrate, and the development processing method is characterized. 15. The developing process comprises a first step of piling a developing solution on a substrate, a second step of statically developing the substrate in the puddle state, and a cleaning solution for the substrate after the static development. And a third step of cleaning the substrate,
15. The development processing method according to claim 14, wherein the addition of the surfactant is performed during the first step. 16. The development processing method according to claim 15, wherein the surfactant is added not only during the first step but also during the third step. 17. The developing process comprises a first step of piling a developing solution on a substrate, a second step of statically developing the substrate in the puddle state, and a cleaning solution for the substrate after the static development. And a third step of cleaning the substrate,
15. The development processing method according to claim 14, wherein the addition of the surfactant is performed during the third step. 18. A development processing method, wherein a resist solution is applied to the surface of a substrate to form a resist film, and a developing solution is supplied onto the formed resist film to develop the substrate. A method for developing treatment, characterized in that the ionic surfactant having a predetermined polarity is mixed with and applied to the surface of the substrate. 19. A development processing method of supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein a predetermined amount is applied to the surface of the resist film before the developing solution is supplied. A development processing method, which comprises supplying an ionic surfactant having polarity. 20. The development process according to claim 14, wherein a polymeric nonionic surfactant is added to the developer instead of the ionic surfactant. Method. 21. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, the charging means charging the surface of the substrate to a zeta potential having a predetermined polarity. A development processing apparatus comprising: 22. The charging means includes a conductive electrode plate,
Voltage applying means for applying a voltage of a predetermined polarity to the electrode plate, the electrode plate is attached to a holding member for holding a substrate, and the substrate is held by the holding member via the electrode plate. 22. The development processing apparatus according to claim 21, wherein the development processing apparatus is provided. 23. The developing processing apparatus according to claim 22, wherein the voltage applying unit includes a control unit that controls a voltage applied to the electrode plate. 24. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein an atmosphere containing ions of a predetermined polarity is provided around the substrate. A development processing apparatus comprising an ion atmosphere supply unit for supplying 25. A developing processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, comprising: a charging member capable of being charged to a predetermined polarity; and the charging member. And a charging member conveying means for conveying and contacting the developing solution on the substrate. 26. The developing processing apparatus according to claim 25, wherein the charging member has the same shape as the substrate. 27. A development processing device for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein an ionic surfactant having a predetermined polarity is supplied onto the substrate. A development processing apparatus, comprising: 28. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein the non-ionic surfactant is supplied onto the substrate. A development processing apparatus comprising a developer supply unit. 29. A developing processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, the charging means charging the developing solution to a zeta potential having a predetermined polarity. A development processing apparatus comprising: 30. The developing processing apparatus according to claim 29, wherein the charging unit includes a device for applying a voltage to a pipe for supplying a developing solution. 31. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, wherein insoluble matter in the developing solution accumulated on the resist film. And a moving member that moves the charging member on the substrate. 32. The charging member is attached to a nozzle for supplying a developing solution onto a substrate,
The development processing apparatus according to claim 31. 33. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to develop the substrate, the concentric circles being provided on an upper surface of a mounting table on which the substrate is mounted. And a plurality of electrodes, a power supply for applying a voltage to each of the electrodes, and a controller for changing the potential of each of the electrodes over time. 34. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to perform development processing on the substrate, comprising a heating device for heating the substrate. Development processor. 35. A development processing method, wherein a resist solution is applied to the surface of a substrate to form a resist film, and a developing solution is supplied onto the formed resist film to develop the substrate. Is conductive, a voltage is applied to the resist film to maintain the resist film at a potential of the same polarity as the insolubilized product in the developing solution at least during the development process. Development processing method. 36. A development processing apparatus for supplying a developing solution onto a resist film formed on a surface of a substrate to perform development processing on the substrate, comprising a mounting table for clamping and holding the substrate.
1. A development processing apparatus, comprising a device for applying a voltage to a resist film on a substrate on the mounting table.