Adhesive bonding and miscellaneous chemical manufacture – Differential fluid etching apparatus – For liquid etchant
Reexamination Certificate
2002-01-17
2003-11-18
Mills, Gregory (Department: 1763)
Adhesive bonding and miscellaneous chemical manufacture
Differential fluid etching apparatus
For liquid etchant
C156S345180, C134S001200, C134S001300
Reexamination Certificate
active
06649018
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the field of manufacturing silicon semiconductors, more specifically to processes and apparatus for removing photoresist from the surfaces of silicon semiconductor wafers during such manufacturing.
BACKGROUND OF THE INVENTION
The importance of clean semiconductor workpiece surfaces in the fabrication of semiconductor microelectronic devices has been recognized for a considerable period of time. Over time, as VLSI and ULSI silicon circuit technology has developed, the cleaning processes have gradually become a particularly critical step in the fabrication process. Trace impurities, such as sodium ions, metals, and particles, are especially detrimental if present on semiconductor surfaces during high-temperature processing because they may spread and diffuse into the semiconductor workpiece and thereby alter the electrical characteristics of the devices formed in the workpiece.
The actual stripping of photoresist from the workpiece is yet another fabrication process that is important to integrated circuit yield, and the yield of other workpiece types. It is during the stripping process that a substantial majority of the photoresist is removed or otherwise disengaged from the surface of the semiconductor workpiece. If the stripping agent is not completely effective, photoresist may remain bonded to the surface. Such bonded photoresist may be extremely difficult to remove during a subsequent cleaning operation and thereby impact the ability to further process the workpiece.
In order to produce a useful semiconductor wafer, first a silicon crystal is grown and then sliced into thin wafers. The thin wafers are then exposed to a photoresist which forms a layer on the wafers. Selected areas of the photoresist are exposed to light, which cures those areas. The remaining unexposed areas of photoresist are then etched off to form patterns on the wafers. Lastly, the wafers are cleaned.
There have been many attempts at improving the speed and efficiency of the removal of the photoresist. For example, Matthews, U.S. Pat. No. 5,776,296, discloses a process for removing photoresist from a semiconductor wafer by diffusing ozone (O
3
) into a bath of deionized water (DI) at sub-ambient temperatures of 1 to 15° C. to form a mixture (DIO
3
). However, the Matthews system and process suffers from certain disadvantages, most especially the low rate of removal of photoresist, as well as a requirement to chill the DI water with a chiller.
It is an object of the present invention to provide a faster and more efficient process of removal of photoresist from a silicon semiconductor wafer than any available in the prior art.
It is another object of the invention to provide an improved apparatus for use in the process which results in and efficient and fast method of removing photoresist from silicon semiconductor wafers.
SUMMARY OF THE INVENTION
These objects, and others which will become apparent from the following detailed description and drawings, are achieved by the present invention which comprises in one aspect applying pressure in excess of one atmosphere to O
3
; mixing the O
3
with DI via a sparger plate to form DIO
3
; and exposing semiconductor wafers having at least one layer of photoresist to said DIO
3
.
In another aspect the invention comprises an apparatus for the removal of photoresist from semiconductor wafers comprising a tank capable of holding semiconductor wafers; a sparger plate set within the tank; a source of O
3
connected to the tank; a source of DI connected to the tank; and a means for recirculating the DI.
The DI water is maintained at ambient or higher temperatures rather than below ambient temperature required by the prior art.
The O
3
is mixed with the DI water so that a high level or concentration of O
3
is present, resulting in DIO
3
water.
It has been found that the agitation of the DIO
3
via a sparger plate increases the velocity of the DIO
3
water and therefore raises the rate of photoresist removal, and thus subambient temperatures are not necessary or desirable. The strip rate for photoresist treated with DIO
3
water is linked to the velocity rate of the DIO
3
water. Notably, an increase in the fluid velocity reduces the boundary layer thickness, thereby resulting in a higher rate of O
3
oxidizing the photoresist, also known as “the etching rate.” In addition, the optional use of sonic energy also reduces the boundary layer thickness, again resulting in a higher rate of O
3
oxidizing the photoresist or etch rate. Thus, the higher the kinetic energy and O
3
concentration, the shorter the strip time.
The etching rate of photoresist utilizing a solution of O
3
in DI water increases linearly with the increase in O
3
concentration. The apparatus of the invention, comprising the sparger, increases the velocity rate of the DIO
3
water so as to reduce the boundary layer thickness and therefore increase the rate of etching.
The method of the invention significantly increases the O
3
concentration in a DI water solution compared to the methods known in the prior art.
The wafers may be placed directly into a tank containing ambient temperature or warmed ozonated water or, preferably, the wafers are placed in a tank of ambient temperature or higher deionized water and ozone is diffused into the tank. Preferably, the ozone is diffused into the water solution for a time sufficient to oxidize substantially all of the organic materials on the wafers. The amount of time needed for diffusion of the ozone into the water will depend on the nature of the organic material being removed and the amount of that material. The specific temperature of the water bath will also affect the time for diffusion of ozone since the amount of absorption of ozone into the water is dependent on the temperature and the oxidation power of the water solution is dependent on the amount of ozone absorbed.
Generally, the ozone will be diffused into the deionized water for about 1 to about 15 minutes. In a preferred embodiment, the ozone is diffused into the deionized water for about 5 to about 10 minutes.
According to the invention process for removing photoresist from semiconductor wafers, pressure in excess of one atmosphere is applied to ozone, the ozone is mixed with deionized water via a sparger plate, and the semiconductor wafers having at least one layer of photoresist are exposed to the mixture of ozone and deionized water.
Preferably the mixture of deionized water and ozone is recirculated and ozone added so that the concentration of ozone in the mixture is about constant.
The mixture of deionized water and ozone is agitated by the sparger plate.
The temperature of the solution of ozone in deionized water in the process tank is preferably above 20-21° C. according to the invention.
The apparatus for removing photoresist from semiconductor wafers comprises a tank capable of holding semiconductor wafers, a sparger plate within the tank, a source of ozone connected to the tank, a source of deionized water connected to the tank, and finally a means for recirculating the deionized water. The apparatus further comprises a pressure plenum connected to the source of ozone. The sparger plate is preferably located on the bottom of the process tank. The means for recirculating the deionized water is preferably connected to the source of the ozone. The means for recirculating the deionized water is preferably connected to a pressure plenum. The apparatus may include a temperature controller which keeps the temperature of the process liquid, DIO
3
, at or above ambient temperature, most preferably at or above 20-21° C.
REFERENCES:
patent: 5464480 (1995-11-01), Matthews
patent: 6080531 (2000-06-01), Carter et al.
patent: 6187216 (2001-02-01), Dryer et al.
Kashkoush Ismail
Novak Richard
Akrion LLC
Belles Brian L.
Fein Michael B.
MacArthur Sylvia R.
Mills Gregory
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