TWI556068B - Methods of laser processing photoresist in a gaseous environment - Google Patents

Description

Laser treatment method using laser in a gas environment

The present invention relates to photoresist processing, and in particular to photoresist processing systems and methods utilizing laser and gaseous environments for improving the characteristics of photoresist.

Photoresist is a photosensitive material used in semiconductor processes. In the process of forming a semiconductor, the photoresist can form small features on the surface of the crucible. As in the process of photolithography, the wafer with the photoresist is placed on the lithography apparatus. Next, a specific pattern to be formed on the germanium wafer is formed on a mask, and then the mask is exposed. Thus, the pattern on the reticle appears on the photoresist, where the photoresist is sensitive to the wavelength of the light. The photoresist can be further divided into a "positive photoresist" and a "negative photoresist". After the positive photoresist is irradiated with light, the exposed region can be removed by exposure processing, and the pattern of the photomask is left on the photoresist. The photoresist is then etched to shift the design pattern on the photoresist to a germanium wafer or other material under the photoresist.

Ideally, the photoresist pattern has dual qualities and a perfect square sidewall. Moreover, the ideal photoresist can accurately replicate the reticle pattern and serve as a perfect etch stop. However, as far as the actual situation is concerned, the sensitivity of the photoresist is limited, and there is some degree of line-edge roughness/LER, and imperfect etching. Barrier layer.

Many efforts have been made to improve photoresist sensitivity, reduce LER, and improve etch resistance. One way is to use sequential infiltration synthesis (SIS). This method utilizes trimethyl aluminum and water at less than 100 ° C in an attempt to improve etch resistance and reduce LER in a few minutes. A reference describing this method is "Enhanced polymeric lithography resists via sequential in circulation synthesis", Tseng et al. (Jounal of Materials Chemistry, 21, 2011 pp. 11722-25. This document is also cited as a Digital Object Identifier. /DOI): 10.1039/c1jm12461g.

However, the few minutes it takes to perform this process will reduce wafer throughput on the production line.

One feature disclosed in the present invention is a method of improving a patterned product wafer. The wafer includes a photoresist layer, wherein the photoresist layer has a surface. This method improves at least one of the etch resistance and the line edge roughness (LER) of the photoresist layer. The method of improving the method comprises: a) exposing the photoresist layer to at least one first process gas selected from the group consisting of trimethyl aluminum gas (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas (TiCl ₄ ), and a group consisting of diethylzinc gas ((C ₂ H ₅ ) ₂ Zn); b) irradiating the photoresist layer and the first process gas with a laser to inject a first gas into the photoresist layer, wherein the photoresist layer The surface temperature is raised to 300 ° C ~ 500 ° C, and the temperature uniformity is +/- 5 ° C; c) the first processing gas remaining around the photoresist layer is removed; d) the photoresist layer is exposed to the second processing gas, wherein The gas comprises water (H ₂ O); e) irradiating the photoresist layer and the second processing gas with a laser to inject a water component (H ₂ O) into the photoresist layer, wherein the surface temperature of the photoresist layer is raised to 300 ° C to 500 °C, and temperature uniformity is +/- 5 °C.

Another feature disclosed herein is the improved method described above, wherein laser illumination comprises scanning the photoresist layer using a laser beam.

Another feature disclosed in the present invention is the above-described improvement method, wherein the laser scanning comprises moving a laser beam, moving a patterned product wafer or co-moving a laser beam and a wafer.

Another feature disclosed in the present invention is the above-described improvement method, wherein the laser beam forms a linear image on the surface of the photoresist layer.

Another feature disclosed in the present invention is the above improvement method, wherein the staying time t of the line image is 1 millisecond (ms) t 100 milliseconds (ms).

Another feature disclosed in the present invention is the above improvement method, wherein the width W and the length L of the line image are respectively 0.2 mm. W 2mm and 10mm L 100mm.

Another feature disclosed in the present invention is the above improvement method, wherein the scanning speed v _s of the line image is 20 mm/s v _s 5000mm/s.

Another feature disclosed in the present invention is the above improvement method, wherein the power density P of the laser beam is 50 watts/mm ² P 150watts/mm ² .

Another feature disclosed in the present invention is the above-described improvement method in which a patterned product wafer is housed in an internal space of a process chamber.

Another feature disclosed in the present invention is the above-described improvement method, which further includes etching the processed patterned product wafer.

Another feature disclosed in the present invention is the above-described improvement method, wherein the steps required to perform steps a) through e) for the entire wafer are 30 to 120 seconds.

Another feature disclosed in the present invention is the above-described improvement method, wherein the number of repetitions of steps a) to e) is one or more. Additionally, each time step e) is completed, a new step of removing the second process gas around the photoresist layer is added.

Another feature disclosed in the present invention is the above-described improvement method in which a product wafer is housed in a process chamber. The improvement method also includes removing the first process gas surrounding the photoresist layer. The removing process includes extracting the first process gas from the process chamber and using an inert gas to purge at least one of the process chambers.

Another feature disclosed in the present invention is a method of processing a product wafer. The product wafer is disposed in an inner space of the processing chamber and has a patterned photoresist layer, wherein the photoresist layer has a surface, wherein the method comprises at least one of an etch resistance and a line edge roughness (LER) of the photoresist layer. Features improved. The steps of the processing method include: a) exposing the surface of the photoresist layer to the first molecular processing gas; b) scanning the surface of the photoresist layer with a laser beam, and injecting molecules of the first molecular gas into the photoresist layer, wherein the light The surface temperature of the resist layer is raised to 300 ° C ~ 500 ° C, and the temperature uniformity is +/- 5 ° C; c) the first molecular processing gas remaining in the internal space of the process chamber is removed; d) the exposed photoresist layer Processing the gas in the second molecule, and repeating step b) for the second molecular processing gas, wherein the first molecular processing gas is selected from the group consisting of trimethyl aluminum gas (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas ( At least one of the group consisting of TiCl ₄ ) and diethylzinc gas ((C ₂ H ₅ ) ₂ Zn), and the second molecular treatment gas includes a water component (H ₂ O).

Another feature disclosed in the present invention is the above processing method, wherein the laser beam forms a line image on the surface of the photoresist layer. The datum time t of the line image is 1ms t 100ms.

Another feature disclosed in the present invention is the above processing method, wherein the width W and the length L of the line image are respectively 0.2 mm. W 2mm and 10mm L 100mm.

Another feature disclosed in the present invention is the above processing method, wherein the scanning speed v _s of the line image is 20 mm/s v _s 5000mm/s.

Another feature disclosed in the present invention is the above processing method, wherein the power density P of the laser beam is 50 watts/mm ² P 150watts/mm ² .

Another feature disclosed in the present invention is the above-described processing method, which further includes etching the processed wafer.

Another feature disclosed in the present invention is the above-described processing method, wherein the steps required to perform steps a) through d) for the entire wafer are 30 to 120 seconds.

Another feature disclosed in the present invention is the above processing method, wherein the process of removing the first molecular processing gas from the internal space of the process chamber includes extracting the first molecular processing gas from the internal space of the processing chamber, and using The inert gas is used to blow at least one of the internal spaces of the process chamber.

Another feature disclosed in the present invention is a method of processing a product wafer. The wafer is disposed in an inner space of the process chamber and has a patterned photoresist layer, wherein the photoresist layer has a surface. This method improves at least one of the etch resistance and the line edge roughness (LER) of the photoresist layer. The steps of the processing method include: a) sequentially injecting the first and second process gases into the internal space of the process chamber, wherein the first injected gas is removed before injecting the subsequent gas; b) using the laser to the light Scanning the surface of the resist layer to sequentially inject the first and second molecular gases into the photoresist layer; c) repeating steps a) and b) multiple times, wherein the first molecular gas is selected from the group consisting of trimethyl aluminum gas At least one of a group consisting of (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas (TiCl ₄ ), and diethylzinc gas ((C ₂ H ₅ ) ₂ Zn), and the second molecule The gas includes water vapor.

Another feature disclosed in the present invention is the above-described processing method for sequentially injecting first and second molecular gases, wherein the laser scanning forms a linear image by a laser beam. The datum time t of the line image is 1ms t 100ms.

Another feature disclosed in the present invention is the above-described processing method for sequentially injecting first and second molecular gases, wherein the width W and length L of the linear image are respectively 0.2 mm. W 2mm and 10mm L 100mm.

Another feature disclosed in the present invention is the above-described processing method for sequentially injecting first and second molecular gases, wherein the scanning speed v _s of the linear image is 20 mm/s. v _s 5000mm/s.

Another feature disclosed in the present invention is the above-described processing method for sequentially injecting first and second molecular gases, wherein the power density P of the laser beam is 50 watts/mm ² P 150watts/mm ² .

Another feature disclosed in the present invention is the above-described processing method for sequentially injecting first and second molecular gases, wherein at least one of the following steps of removing the first or second molecular gas from the internal space of the processing chamber : i) extracting the first or second molecular gas from the internal space of the process chamber; and ii) purging the internal space of the process chamber with an inert gas.

Another feature disclosed in the present invention is a method of processing a product wafer. The wafer is disposed in an inner space of the process chamber and has a patterned photoresist layer, wherein the photoresist layer has a surface. This method improves at least one of the etch resistance and the line edge roughness (LER) of the photoresist layer. The steps of the processing method include: a) exposing the surface of the photoresist layer to the first process gas, wherein the first process gas comprises molecules, and the molecules are selected from the group consisting of trimethyl aluminum (Al ₂ (CH ₃ ) ₆ ) gas, four At least one gas in a molecular group consisting of titanium chloride (TiCl ₄ ) gas and diethyl zinc ((C ₂ H ₅ ) ₂ Zn) gas; b) using a laser beam to irradiate the surface of the photoresist layer Scanning, the molecules of the first process gas are injected into the photoresist layer, wherein the surface temperature of the photoresist layer is raised to 300 ° C ~ 500 ° C, and the temperature uniformity is +/- 5 ° C.

Another feature disclosed in the present invention is the above-described processing method using a molecular injection photoresist layer. After the step b), the method further includes the steps of: c) removing the first processing gas in the internal space of the processing chamber; d) Exposing the photoresist layer to the second process gas, wherein the second process gas comprises water (H ₂ O) molecules; e) scanning the surface of the photoresist layer with a laser beam to inject water (H ₂ O) molecules into the photoresist Floor.

Another feature disclosed in the present invention is the above-described processing method using a molecular injection photoresist layer, wherein the process of removing the first process gas from the internal space of the process chamber includes at least one of the following techniques: i) from the process chamber The internal space extracts the first or second molecular processing gas; and ii) uses an inert gas to purge the internal space of the process chamber.

Another feature disclosed in the present invention is the above-described processing method using a molecular injection photoresist layer in which a laser beam forms a linear image. The datum time t of the line image is 1ms t 100ms.

Another feature disclosed in the present invention is the above-described processing method using a molecular injection photoresist layer, wherein the width W and the length L of the linear image are respectively 0.2 mm. W 2mm and 10mm L 100mm, linear image scanning speed v _s is 20mm / s v _s The power density P of the laser beam of 5000 mm/s is 50 watts/mm ² P 150watts/mm ² .

Another feature disclosed in the present invention is the above-described processing method using a molecular injection photoresist layer, wherein the steps required to perform steps a) and b) for the entire wafer are 30 to 120 seconds.

The detailed features and advantages of the present invention are set forth in the Detailed Description of the Detailed Description of the <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> </ RTI> <RTIgt; The objects and advantages associated with the present invention can be readily understood by those skilled in the art. The above summary of the invention and the following detailed description are merely exemplary, and are intended to provide an overview or architecture to understand the attributes and characteristics of the patent scope.

10‧‧‧Product Wafer

20‧‧‧Substrate

22‧‧‧ upper surface

30‧‧‧Photoresist layer

32‧‧‧ top surface

TH‧‧‧ thickness

40‧‧‧Exposure area

44‧‧‧Integrated circuit chip

50‧‧‧ graphics

100‧‧‧ Laser Processing System

104‧‧‧Environmental environment

110‧‧‧Processing cavity

112‧‧‧Internal space

114‧‧‧ top wall

116‧‧‧Form

130‧‧‧ Wafer Platform

132‧‧‧ chuck

134‧‧‧ platform actuator

136‧‧‧ board

150A‧‧‧First process gas source

152A‧‧‧First process gas

150B‧‧‧second source of process gas

152B‧‧‧second process gas

160‧‧‧vacuum system

170‧‧‧Inert gas source

172‧‧‧Inert gas

180‧‧‧Laser system

AR‧‧‧ arrow

182‧‧‧Laser beam

182L‧‧‧ linear image

N‧‧‧Vertical direction

Α‧‧‧incidence angle

W‧‧‧Width

L‧‧‧ length

200‧‧‧ controller

220‧‧‧Air curtain

The accompanying drawings are provided to provide a further understanding of the invention and are incorporated The drawings illustrate one or more embodiments, and together with the detailed description A more complete understanding of the present invention can be obtained from the following description and drawings.

[Fig. 1] is a cross-sectional view of a wafer including a tantalum substrate coated with a photoresist layer.

[Fig. 2] is a plan view of the wafer in Fig. 1 showing the exposure fields of the wafer and the included patterns.

[Fig. 3] is a schematic diagram of a laser processing system for performing a wafer processing method, thereby improving at least etch resistance and line edge roughness (LER) of the photoresist layer. A feature.

[Fig. 4] is a vertical view of a linear image formed by a laser beam on the surface of the photoresist layer and having a width W and a length L.

[Fig. 5] is a plan view of a photoresist layer of a wafer, which is subjected to a laser scanning step.

[Fig. 6] is a schematic view similar to Fig. 3, showing another embodiment of the process chamber Process chamber.

The following are detailed references to various embodiments of the invention, which are illustrated by the accompanying drawings. Wherever possible, the same or similar reference numerals reference The attached drawings are not to scale. Those skilled in the art will recognize the main features of the invention from the simplified drawings.

The following patent ranges are incorporated into and incorporated by reference.

Any documents or patent documents disclosed herein are included in the references.

For illustration purposes, some patterns use Cartesian coordinates, but are not intended to limit direction or position.

1 and 2 are a cross-sectional view and a plan view, respectively, of the product wafer 10. Wafer 10 includes a tantalum substrate 20, wherein substrate 20 has an upper surface 22. The photoresist layer 30 is applied to the upper surface 22 of the substrate 20, wherein the photoresist layer 30 has a top surface 32 and a thickness TH. Please refer to FIG. 2, in which wafer 10 includes an array of exposure fields ("regions") 40. The region 40 is formed by the photoresist layer 30 exposing layer by region or a single multiple region. For example, each exposure area 40 includes a plurality of sub-areas. These sub-regions are used to define the boundaries of the integrated circuit wafer 44 (as shown in the first close-up) when the wafer process is completed. The wafer 10 shown in the drawings represents a semiconductor wafer in an integrated circuit process.

The photoresist layer 30 records the pattern features transferred by the photolithography reticles in the respective exposure regions 40 through a lithography image system, or a lithography apparatus as is commonly referred to in the industry. An example of a lithography apparatus is described in U.S. Patent 6,879,383. Then, when all of the exposed regions 40 have been formed, the wafer 10 is regarded as an exposed state.

The exposed wafer 10 is further developed to develop the exposed portion of the photoresist layer 30 (when the photoresist layer 30 is a positive photoresist). The results produced by the above process are as shown in the second close-up view of FIG. 2, in which each of the exposed regions 40 includes the same three-dimensional resist pattern 50. The wafer 10 in its current state during this process may be referred to as a "patterned product wafer."

In general, the next step in the round process is to etch the patterned product wafer. The etching transfers the pattern 50 of the photoresist 30 to the germanium substrate 20. In this step, the photoresist pattern 50 acts as an etch-stopping structure.

As previously described, the photoresist layer 30 has, among other things, performance limitations associated with etch resistance and line edge roughness.

Please refer to FIG. 3, which is a schematic cross-sectional view of the laser processing system 100. The laser processing system 100 is used to process the patterned product wafer 10 to improve the performance of the photoresist layer 30. The performance obtained by the photoresist layer 30 is improved to at least one of etching resistance and line edge roughness. This pattern distinguishes from a non-processed patterned product wafer 10.

Laser processing system 100 includes a process chamber 110. The process chamber 110 is provided with an interior space 112. The interior space 112 is sufficient to accommodate the patterned product wafer 10. The process chamber 110 includes a top wall 114 with a top wall 114 having a window 116. The light transmission wavelength range of the window 116 is Δλ. The wavelength range Δλ includes the processing wavelength λ which will be discussed below. In one example, the material used for the window 116 is quartz glass. The laser processing system 100 is disposed within the ambient environment 104. The process chamber 110 is designed to provide a control environment in the interior space 112 to process the photoresist layer 30 (as described below).

The patterned product wafer 10 is supported by the wafer platform 130 in the process chamber 110 is in the internal space 112. In one example, wafer platform 130 can be moved in the x, y, and z directions. Wafer platform 130 can also be rotated on the x, y, and z axes if desired. The wafer platform 130 is coupled to the platform actuator 134 for operation.

Laser processing system 100 also includes at least one source of process gas sources 150A and 150B. The process gas sources 150A and 150B flow control connect the internal space 112 of the process chamber 110 and release at least one of the process gases 152A and 152B. In one example, at least one of the process gases 152A and 152B is a molecular gas. In the laser processing system 100 of FIG. 3, the process gas sources 150A and 150B that release the process gases 152A and 152B, respectively, are presented by way of example. In one example, the first process gas 152A is a molecular gas selected from the group consisting of trimethyl aluminum (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride (TiCl ₄ ), and diethyl zinc ((C ₂ H _{5 ) 2} Zn) at least one molecular gas in the group consisting of. In another embodiment, the second molecular treatment gas 152B includes water vapor (ie, H ₂ O gas). In one example, the water vapor can be a component of air or other gas rather than pure water vapor.

The laser processing system 100 also includes a vacuum system 160 fluidly coupled to the interior space 112 of the process chamber 110. The purpose of the vacuum system 160 is to remove any gas in the interior space 112 of the process chamber 110 at a particular time while processing the patterned product wafer 10.

The laser processing system 100 also includes an inert gas source 170 fluidly coupled to the interior space 112 of the process chamber 110. The inert gas source 170 can provide an inert gas 172 to purge the first process gas 152A or the second process gas 152B. In one example, the inert gas 172 is nitrogen. Therefore, the process gas 152A or 152B around the photoresist layer 30 can be removed, so that these gases can no longer chemically react with the photoresist layer 30.

Laser processing system 100 also includes a laser system 180. Laser system 180 is used A laser beam 182 having a processing wavelength λ is produced. In one example, laser beam 182 can be scanned as indicated by arrow AR. The laser processing system 100 can include a beam conditioning optics (not shown). The beam concentrating mirror can include beam scanning elements and components such as scanning mirrors.

Fig. 4 is an elevational view of an exemplary linear image 182L. As described below, the line image 182L is formed by the laser beam 182 intersecting the top surface 32 of the photoresist layer 30. The line image 182L has a width W and a length L, wherein the W and L lines are determined by the incident angle α of the light beam with respect to the vertical direction N of the top surface 32 of the photoresist layer 30.

In one example, laser system 180 produces a laser beam 182 having the following parameters, as shown in Table 1.

In Table 1, the dwell time t represents the fixed time at which the line image 182L stays on the top surface 32 of the photoresist layer 30. The scanning speed v _s represents the moving speed of the line image 182L on the top surface 32 of the photoresist layer 30. Referring to Figure 5, a plan view of the patterned product wafer 10 is shown. This figure illustrates how the line image 182L moves on the top surface 32 of the photoresist layer 30. With respect to the top surface 32 of the photoresist layer 30, the movement of the line image 182L can be achieved by moving the laser beam 182 (scanning); moving the wafer platform 130; and a combination of the two. In one example, the laser beam 182 is a back-and-forth reciprocating scan method, such as a botanic burstrophed or raster-scan.

The laser processing system 100 also includes a controller 200. The controller 200 operates the connection: at least one gas source of the first and second process gas sources 150A and 150B; a platform actuator 134; a vacuum system 160; an inert gas source 170; and a laser system 180. When the laser processing system 100 processes the patterned product wafer 10, the above design gives the controller 200 control of the overall operation of the laser processing system 100. In one example, controller 200 is or includes a computer, such as a personal computer or workstation. The controller 200 preferably includes any number of commercial grade microprocessors, suitable bus system architectures (connecting the microprocessor to a memory device, such as a hard disk), and suitable input devices (such as a keyboard) and output devices (such as a display). . The controller 200 can be built into a computer readable medium (such as a memory, a processor, or both) via a software command in a programmed manner to perform various functions of the laser processing system 100, thereby implementing a patterned product. Wafer 10 is processed.

The operational steps of the processing of the patterned product wafer 10 by the laser processing system 100 will be discussed below. Step 1 is to operate the vacuum system 160 to remove ambient gases in the interior space 112 of the process chamber 110 to establish an initial state of the process. For example, the oxygen density in the interior space 112 of the process chamber 100 is less than 100 ppm (parts per million). After the initial state is established, step 2 is to inject the first process into the internal space 112 of the process chamber 100. Gas 152A, wherein first process gas 152A contacts top surface 32 of photoresist layer 30.

Next, in step 3, the laser beam 182 scans the patterned product wafer 10 (eg, raster scan). That is, the line image 182L is struck on the top surface 32 of the photoresist layer 30 via the laser beam 182. In one example, the laser scanning process increases the temperature of the photoresist layer 30 to 300 ° C to 500 ° C and the temperature uniformity is +/- 5 ° C. This phenomenon causes the molecules of the first process gas 152A to be injected into the photoresist layer 30. According to the parameter data listed in Table 1, it takes about 30 to 120 seconds to scan the entire patterned product wafer 10. This time range is referred to as "wafer processing time" in this specification.

The portions of the wafer processing method or process discussed below are similar to atomic layer deposition (ALD). That is to say, a monoatomic layer of a material is deposited on the surface and a chemical reaction is generated, which in turn affects some substances on the surface and under the surface. As far as is known, the injection of trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) causes an improvement in the etching resistance of the photoresist layer 30. However, as previously discussed, in the process of the prior art, the step of gas injection of photoresist is performed at slow speed and low temperature conditions. The difference is that the completion time of the injection step of the present invention takes only a few milliseconds (ms).

It is important to note that the short dwell time t of the line image 182L (via the laser beam) prevents the flow of the photoresist layer 30, thereby maintaining the photoresist pattern 50. It can be seen that the surface temperature of the photoresist layer 30 is increased by the laser beam 182, thereby causing the ALD-form material to be deposited in the top surface 32 or the photoresist layer 30 of the photoresist layer 30.

When the laser beam 182 completes scanning the top surface 32 of the photoresist layer 30 in the form of a line image 182L (please refer to FIG. 5), the next step is step 4. Step 4 is to remove the first process gas 152A remaining around the photoresist layer 30. The removal may evacuate the interior space 112 of the process chamber 110 through the vacuum system 160. Another option is, or with vacuum The system 160 cooperates to activate the inert gas source 170 to purge the interior space 112 of the process chamber 110 using the inert gas 172.

Then, step 5 (optionally, depending on the type of first process gas used) is injected into the interior space 112 of the process chamber 110 to inject the second process gas 152B. As noted above, in one example, the second process gas 152B is a molecular vapor containing water vapor (H ₂ O).

Next, in step 6, the laser beam 182 scans the top surface 32 of the photoresist layer 30 in the form of a line image 182L, causing water molecules (H ₂ O) to be injected into the photoresist layer 30. In step 7, the residual second process gas 152B in the interior space 112 of the process chamber 110 is removed by a technique as described above.

Steps 2 to 7 can be repeatedly performed until at least one of the etch resistance and the line edge roughness (LER) of the photoresist layer 30 is improved to a desired degree.

In an embodiment, the following types of first process gas 152A and second process gas 152B may be used: (1) trimethylaluminum (Al ₂ (CH ₃ ) ₆ ) and water vapor to inject aluminum or sapphire (Al ₂ O) ₃ ); (2) titanium tetrachloride (TiCl ₄ ) and water vapor to inject titanium (Ti) or titanium oxide (TiO); (3) and diethyl zinc ((C ₂ H ₅ ) ₂ Zn) and Water vapor is injected into zinc or zinc oxide (ZnO).

The second process gas 152B of the water vapor type is used to form a metal oxide. For example, to form an etch barrier, trimethylaluminum (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride (TiCl ₄ ) or zinc dichloride ((C ₂ H ₅ ) ₂ Zn) The photoresist layer 30 is implanted, but the second process gas 152B is not implanted.

Referring to Figure 6, it is similar to Figure 3 and presents another embodiment of a laser processing system 100. The process chamber 110 in this embodiment is presented in the form of a micro-process chamber. It is disclosed in "Microchamber" of U.S. Patent No. 5,997,963 and "Movable microchamber with gas curtain" of U.S. Patent Application Serial No. 13/690,132. In this embodiment, the wafer platform 130 supports the chuck 132. The chuck 132 further supports the patterned product wafer 10. The movable wafer platform 130 is supported by the mobility of the carriage 136. The top wall 114 includes a window 116 that is sized to pass the laser beam 182 through the window 116. In one example, the laser beam 182 strikes the incident angle of the photoresist layer 30 at a non-normal incidence.

In one example, the laser processing system 100 also employs a curtain 220 to prevent gases (such as oxygen) from the surrounding environment 104 from entering the interior space 112 of the process chamber 110. In contrast, in one example, the process chamber 110 is not isolated from the surrounding environment. If the configuration of the process chamber 110 is a micro-machining chamber, the internal space 112 can be filled with a specific gas (the first or second process gas 152A or 152B) to discharge the original gas in the internal space 112. In one example, the laser processing system 100 uses an inert gas 172 of inert gas source 170 to remove the original gas (e.g., air) or the first process gas 152A or the second process gas 152B during processing.

When the patterned product wafer 10 is processed by one of the methods described above, the etch resistance and the line edge roughness of the photoresist layer 30 compared to the unprocessed patterned product wafer 10. At least one of the characteristics of (LER) can be improved. Here, the processed patterned product wafer 10 can enter a standardized semiconductor etching process to form a semiconductor device.

It will be apparent to those skilled in the art that various modifications of the preferred embodiments of the invention may be made without departing from the spirit and scope of the invention. Therefore, variations and modifications encompassed by the concepts of the appended claims are included in the present invention. And the same concept.

10‧‧‧Product Wafer

20‧‧‧Substrate

30‧‧‧Photoresist layer

32‧‧‧ top surface

100‧‧‧ Laser Processing System

104‧‧‧Environmental environment

110‧‧‧Processing cavity

112‧‧‧Internal space

114‧‧‧ top wall

116‧‧‧Form

130‧‧‧ Wafer Platform

134‧‧‧ platform actuator

150A‧‧‧First process gas source

150B‧‧‧second source of process gas

152A‧‧‧First process gas

152B‧‧‧second process gas

160‧‧‧vacuum system

170‧‧‧Inert gas source

172‧‧‧Inert gas

180‧‧‧Laser system

182‧‧‧Laser beam

182L‧‧‧ linear image

200‧‧‧ controller

AR‧‧‧ arrow

Claims (33)

A method of improving a patterned product wafer, the wafer comprising a photoresist layer having a surface for improving etch resistance and line edge roughness of the photoresist layer At least one of roughness/LER), the improvement method comprises: a) exposing the photoresist layer to at least one first process gas, wherein the at least one first process gas is selected from the group consisting of trimethylaluminum gas ( a group of Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas (TiCl ₄ ), and diethylzinc gas ((C ₂ H ₅ ) ₂ Zn); b) irradiating the photoresist layer with a laser And the at least one first processing gas, the at least one first processing gas is injected into the photoresist layer, wherein the temperature of the surface is raised to 300 ° C ~ 500 ° C, and the temperature uniformity is +/- 5 ° C; c) shift Excepting the at least one first process gas remaining around the photoresist layer; d) exposing the photoresist layer to a second process gas containing water (H ₂ O); and e) irradiating the photoresist layer with a laser and said second process gas, a moisture (H ₂ O) was injected into the photoresist layer, wherein the temperature of the surface of the resist layer to lift 300 ℃ ~ 500 ℃, and temperature A uniformity of +/- 5 ℃. The improvement method of claim 1, wherein in the step b) and the step e), the laser irradiation comprises scanning the surface of the photoresist layer using a laser beam. The improvement method of claim 2, wherein scanning comprises moving the laser beam, moving the patterned product wafer, or moving the laser beam and the patterned product wafer together. The improvement method of claim 2, wherein the laser beam forms a line image on the surface of the photoresist layer. The improvement method of claim 4, wherein the linear image has a dwell time of t, wherein 1 ms t 100ms. The improvement method of claim 4, wherein the linear image has a width W and a length L, wherein 0.2 mm W 2mm and 10mm L 100mm. The improvement method of claim 4, wherein the scanning speed of the linear image is v _s , wherein 20 mm/s v _s 5000mm/s. The improvement method of claim 2, wherein the laser beam has a power density of P, wherein 50 watts/mm ² P 150watts/mm ² . The improvement method of claim 1, wherein the patterned product wafer is housed in an internal space of a process chamber. The improvement method of claim 1, further comprising etching the processed patterned product wafer. The improvement method according to any one of claims 1 to 10, wherein steps a) to e) occupy the processing time of 30 to 120 seconds throughout the wafer processing time. The improvement method of claim 1, wherein the number of repetitions of steps a) to e) is one or more, and a new step is added after each step e), the new step is to remove the periphery of the photoresist layer Second process gas. The improvement method of claim 1, wherein the patterned product wafer is housed in an internal space of a process cavity, and the step of removing the first process gas around the photoresist layer comprises from the process cavity The interior space evacuates the first process gas; and an inert gas purges at least one of the interior spaces of the process chamber. A method for processing a product wafer, wherein the wafer has a patterned photoresist layer, the patterned photoresist layer has a surface, and the wafer is located in an internal space of a process cavity, and the processing method is used to improve the At least one of an etch resistance and a line-edge roughness/LER of the photoresist layer, the processing method comprising: a) exposing the surface of the patterned photoresist layer to a surface a first molecular processing gas; b) scanning the surface of the patterned photoresist layer with a laser beam, and injecting molecules of the first molecular processing gas into the patterned photoresist layer, wherein the patterned photoresist layer The surface temperature is raised to 300 ° C ~ 500 ° C, and the temperature uniformity is +/- 5 ° C; c) the first molecular processing gas remaining in the internal space of the process chamber is removed; and d) the pattern is exposed The photoresist layer is in a second molecular processing gas, and step b) is repeated for the second molecular processing gas, wherein the first molecular processing gas is selected from the group consisting of trimethyl aluminum gas (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas (TiCl ₄ ) and diethyl zinc gas ( At least one of the group consisting of (C ₂ H ₅ ) ₂ Zn), and the gas in the second molecule contains moisture (H ₂ O). The processing method of claim 14, wherein the laser beam forms a line image on the surface of the photoresist layer, and the line image has a d time of t, wherein 1 ms t 100ms. The processing method of claim 15, wherein the linear image has a width W and a length L, wherein 0.2 mm W 2mm and 10mm L 100mm. The processing method of claim 15, wherein the scanning speed of the line image is v _s , wherein 20 mm/s v _s 5000mm/s. The processing method of claim 14, wherein the power density of the laser beam is P, wherein 50 watts/mm ² P 150watts/mm ² . The processing method of claim 14, further comprising etching the processed patterned product wafer. The processing method of claim 14, wherein the processing time occupied by steps a) to d) is 30 to 120 seconds throughout the wafer processing time. The processing method of claim 14, wherein the removing the first molecular processing gas in the internal space of the processing chamber comprises extracting the first molecular processing gas from the internal space of the processing chamber; The gas purges at least one of the interior spaces of the process chamber. A method for processing a product wafer, the wafer having a patterned photoresist layer having a surface, and the wafer is located in an internal space of a process cavity, the processing method for improving the light At least one of an etch resistance and a line-edge roughness of the resist layer, the processing method comprising: a) sequentially injecting a first molecular processing gas and a second The molecular processing gas is in the internal space of the processing chamber, and includes removing the previously injected first or second molecular processing gas before injecting the subsequent first or second molecular processing gas; b) using the laser beam Scanning the surface of the patterned photoresist layer to sequentially inject the first and second molecular processing gases into the patterned photoresist layer; and c) repeating steps a) and b) a plurality of times, wherein the first molecule The treatment gas is selected from the group consisting of trimethylaluminum gas (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas (TiCl ₄ ), and diethylzinc gas ((C ₂ H ₅ ) ₂ Zn). At least one of the group, and the second molecular processing gas comprises water vapor. The processing method of claim 22, wherein the laser scanning forms a line image by a laser beam, and the line image has a d time of t, wherein 1 ms t 100ms. The processing method of claim 23, wherein the linear image has a width W and a length L, wherein 0.2 mm W 2mm and 10mm L 100mm. The processing method of claim 23, wherein the scanning speed of the line image is v _{s of} which 20 mm/s v _s 5000mm/s. The processing method of claim 23, wherein the power density of the laser beam is P, wherein 50 watts/mm ² P 150watts/mm ² . The processing method of claim 23, wherein the step of removing the first or second molecular gas in the internal space of the processing chamber comprises: i) extracting the first or the internal space from the processing chamber a second molecular processing gas; and ii) an inert gas to purge at least one of the interior spaces of the process chamber. A product wafer processing method, the wafer has a patterned photoresist layer, the patterned photoresist layer has a surface, and the wafer is located in an internal space of a process cavity, and the processing method is used to improve the photoresist At least one of an etch resistance and a line-edge roughness/LER of the layer, the processing method comprising: a) exposing the surface of the patterned photoresist layer to the first process In the gas, the first processing gas comprises a plurality of molecules selected from at least one of trimethyl aluminum gas (Al ₂ (CH ₃ ) ₆ ), titanium tetrachloride gas (TiCl ₄ ), and diethyl At least one of the group consisting of zinc gas ((C ₂ H ₅ ) ₂ Zn); and b) scanning the surface of the patterned photoresist using a laser beam to cause the first process gas The molecules are injected into the patterned photoresist layer, wherein the temperature of the surface of the photoresist layer is raised to 300 ° C to 500 ° C, and the temperature uniformity is +/- 5 ° C. The processing method of claim 28, after step b), further comprising the steps of: c) removing the first processing gas in the internal space of the processing chamber; and d) exposing the photoresist layer to a second processing gas Wherein the second process gas comprises water molecules (H ₂ O); and e) scanning the surface of the photoresist layer with a laser beam to inject water molecules (H ₂ O) into the photoresist layer. The processing method of claim 29, wherein the removing the first processing gas in the internal space of the processing chamber comprises at least one of: i) extracting the first space in the internal space of the processing chamber a process gas; and ii) blowing the interior space of the process chamber with an inert gas. The processing method of claim 28, wherein the laser beam forms a line image, and the line image has a dwell time of t, wherein 1 ms t 100ms. The processing method of claim 31, wherein the linear image has a width W and a length L, a scanning speed of the laser beam is v _s , and a power density of the laser beam is P, wherein 0.2 mm W 2mm, 10mm L 100mm, 20mm/s v _s 5000mm/s and 50watts/mm ² P 150watts/mm ² . The processing method of claim 28, wherein the processing time occupied by steps a) and b) during the entire processing time of the wafer is 30 to 120 seconds.