CN115793416B - Method for manufacturing semiconductor device and method for monitoring impurities of photolithography process chemicals - Google Patents
Method for manufacturing semiconductor device and method for monitoring impurities of photolithography process chemicals Download PDFInfo
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Abstract
The invention provides a method for monitoring impurities in a photolithography process chemical, which comprises the following steps of: providing a bare wafer; coating a layer of coating on the surface of the bare wafer, wherein the coating is a hexamethyldisilazane coating so that the surface of the bare wafer is in a hydrophobic state; coating the surface of the coating with chemicals to be monitored; bare wafers coated with chemicals on the coating were measured using a measuring machine to monitor the hydrophobic impurities in the chemicals. The surface of the bare wafer adsorbs water molecules, and a layer of hexamethyldisilazane coating HMDS is coated on the surface of the bare wafer, so that the HMDS replaces adhesion between water and an oxide layer on the surface of the bare wafer to form a coating which is easy to adsorb hydrophobic substances, and therefore, after chemicals are coated on the coating, hydrophobic impurities in the chemicals can be effectively adsorbed, meanwhile, other elements which are not needed by semiconductor products are not introduced in the monitoring process, and secondary pollution is prevented.
Description
Technical Field
The invention relates to the technical field of semiconductor photoetching technology, in particular to a semiconductor device preparation method and a method for monitoring impurities of photoetching technology chemicals.
Background
In the semiconductor manufacturing process, the photolithography technology is one of the key technologies of the integrated circuit, is an important economic impact factor in the whole product manufacturing, and the photolithography cost occupies 35% of the whole manufacturing cost. Photolithography is also an important reason for determining the evolution of integrated circuits according to moore's law, and without advancement of photolithographic techniques, integrated circuits cannot go from microns to deep submicron to the nanoera. The general photoetching process mainly comprises three main processing steps of gluing, exposing and developing, namely, firstly, uniformly coating photoresist on the surface of a substrate, then exposing a mask pattern through an exposing machine, and finally, realizing the transfer of the mask pattern from a mask plate to the substrate through developing.
Chemicals suitable for photolithography processes are frequently and largely used during photolithography, and impurities may be introduced into the chemicals themselves or during transportation thereof, for example, in pipeline transportation, which may have a great influence on the quality of photolithography processes. Thus, during the lithographic process, the chemicals used are monitored for contaminants, i.e. for impurities. The existing monitoring method is to coat chemicals to be monitored on a bare wafer, and measure impurity results by a measuring machine after the coating is finished, but the accuracy of the method for monitoring the impurities is not high, and the impurities in the chemicals cannot be comprehensively monitored, so that the effect of the subsequent photoetching process is affected.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for manufacturing a semiconductor device and a method for monitoring impurities in a chemical for a photolithography process, which are used for solving the problems that in the prior art, the accuracy of monitoring impurities in a chemical used in the photolithography process is not high, and impurities in the chemical cannot be monitored comprehensively, so that effects of a subsequent photolithography process are affected, and the like.
To achieve the above and other related objects, the present invention provides a method of monitoring impurities in a photolithography process chemical, the method of monitoring impurities in the chemical comprising monitoring hydrophobic impurities in the chemical;
the method for monitoring the hydrophobic impurities in the chemical comprises the following steps:
providing a bare wafer;
coating a layer of coating on the surface of the bare wafer, wherein the coating is a hexamethyldisilazane coating so that the surface of the bare wafer is in a hydrophobic state;
coating the surface of the coating with chemicals to be monitored;
the bare wafer coated with the chemical on the coating is measured using a measuring machine to monitor hydrophobic impurities in the chemical.
Optionally, the parameters of the hexamethyldisilazane coating are: the pH value is between 8.4 and 8.6, and the density is between 0.7kg/m 3 ~0.8kg/m 3 The concentration is more than 99 percent; the coating speed is 2300 ml/min-2600 ml/min, and the dosage is 1400 ml-160 ml.
Further, parameters of the hexamethyldisilazane coating are: pH 8.5, density 0.77kg/m 3 Concentration > 99%; the coating speed was 2500ml/min and the amount was 1500ml.
Optionally, the chemicals include at least one of photoresist, thinner, ultrapure water, and developer required for the photolithography process.
Optionally, the method of monitoring the impurity of the chemical further comprises monitoring the hydrophilic impurity in the chemical.
Further, the method for monitoring hydrophilic impurities in the chemical comprises: prior to applying the coating: coating the surface of the bare wafer with the chemical; measuring the bare wafer coated with the chemical by using a measuring machine to monitor hydrophilic impurities in the chemical; and finally, cleaning the chemical coated on the surface of the bare wafer.
Optionally, after the bare wafer is provided, measuring the bare wafer by using a measuring machine to monitor impurities on the bare wafer to obtain a first impurity value; after the surface of the bare wafer is coated with the coating, measuring the bare wafer coated with the coating by using a measuring machine to monitor impurities on the bare wafer and the coating so as to obtain a second impurity value; and obtaining the impurity of the coating by subtracting the first impurity value from the second impurity value.
Further, the chemical is transported through a pipeline.
Optionally, the hydrophobic impurity comprises lead.
The invention also provides a semiconductor device manufacturing method, which comprises the method for monitoring the impurities of the photoetching process chemicals.
As described above, according to the method for monitoring chemical impurities in the photoetching process, the surface of the bare wafer adsorbs water molecules, and the HMDS replaces adhesion between water and an oxide layer on the surface of the bare wafer by coating a layer of HMDS on the surface of the bare wafer, so that a coating layer which is easy to adsorb hydrophobic substances is formed, so that after the chemical is coated on the coating layer, the hydrophobic impurities in the chemical can be effectively adsorbed, meanwhile, other elements which are not needed by semiconductor products are not introduced in the monitoring process, and secondary pollution is prevented. The monitoring method can be used for directly monitoring the hydrophobic impurities in the chemicals, and generally the chemicals are purchased, and an upstream manufacturer can provide the purity of the chemicals, so that the monitored hydrophobic impurities can be judged as the hydrophobic impurities introduced into the pipeline when the purchased chemicals are transmitted to a process node through the pipeline, namely the pipeline is reminded of the need of impurity removal.
Drawings
FIG. 1 is a schematic view showing the results of an optical microscope for monitoring impurities on hexamethyldisilazane coating in the method for monitoring impurities of photolithography process chemicals according to the present invention.
Fig. 2 is a schematic diagram showing the result of an optical microscope for monitoring hydrophobic impurities in a mixed chemical of ultrapure water and a developer in the method for monitoring impurities in a photolithography process chemical according to the present invention.
Fig. 3 is a schematic diagram of electron microscope results for monitoring hydrophobic impurities in the mixed chemical of ultrapure water and a developer of fig. 2.
Fig. 4 is a schematic diagram showing the results of component analysis under an electron microscope of hydrophobic impurities in the mixed chemical of ultrapure water and a developer of fig. 2.
FIG. 5 shows a schematic diagram of the chemical reaction of HMDS with water.
Description of the embodiments
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Please refer to fig. 1 to 5. It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention are shown in the drawings rather than the number, shape and size of the components in actual implementation, and the form, number and proportion of each component in actual implementation may be arbitrarily changed, and the layout of the components may be more complex.
As described in the background art, impurities may be introduced into the chemical itself during the photolithography process or during the transfer process, so that the impurities in the chemical or the chemical transfer line may be monitored in advance by monitoring the impurities in the chemical before the photolithography process. However, the current monitoring method cannot fully monitor impurities in chemicals, so that the effect of the subsequent photolithography process is affected. The inventors have studied so far to find that this problem arises because the existing monitoring methods are mainly directed to the monitoring of hydrophilic impurities, and neglecting the monitoring of hydrophobic impurities.
Based on this, the present embodiment provides a method of monitoring impurities in a photolithography process chemistry, the method comprising monitoring hydrophobic impurities in the photolithography process chemistry; the method for monitoring the hydrophobic impurities in the chemical comprises the following steps:
providing a bare wafer;
coating a layer of coating on the surface of the bare wafer, wherein the coating is a hexamethyldisilazane coating so that the surface of the bare wafer is in a hydrophobic state;
coating the surface of the coating with chemicals to be monitored;
the bare wafer coated with the chemical on the coating is measured using a measuring machine to monitor hydrophobic impurities in the chemical.
It should be noted that the bare wafer is typically a chemical test wafer, and is not subjected to any product process thereon, and the material of the bare wafer is consistent with the material of the wafer used in the subsequent photolithography process, typically a semiconductor material such as silicon, germanium, etc. The surface of the bare wafer adsorbs water molecules, and by coating a layer of hexamethyldisilazane coating on the surface of the bare wafer, hexamethyldisilazane is called HMDS for short, and the molecular formula of the hexamethyldisilazane is (Si (CH 3) 3 ) 2NH, colorless clear liquid, as shown in figure 5, HMDS replaces bonding between water and an oxide layer on the surface of a bare wafer to form a coating which is easy to adsorb hydrophobic substances, so that after the coating is coated with chemicals, hydrophobic impurities in the chemicals can be effectively adsorbed, meanwhile, unnecessary elements of other semiconductor products can not be introduced in the monitoring process, and secondary pollution is prevented. The method can be used for directly monitoring hydrophobic impurities in chemical products, and general chemical productsThe purity of the chemical is provided by an upstream manufacturer in a purchasing mode, so that the hydrophobic impurities monitored when the purchased chemical is transmitted to a process node through a pipeline can be judged as the hydrophobic impurities introduced into the pipeline, namely, the pipeline is reminded of needing impurity removal.
In this embodiment, the parameters of the hexamethyldisilazane coating are selected as follows: the pH value is between 8.4 and 8.6, and the density is between 0.7kg/m 3 ~0.8kg/m 3 The concentration is more than 99 percent; the coating speed is 2300 ml/min-2600 ml/min, and the dosage is 1400 ml-1600 ml; the optimal parameters are: pH 8.5, density 0.77kg/m 3 Concentration > 99%; the coating speed was 2500ml/min and the amount was 1500ml.
The chemicals mainly used in the photolithography process include photoresist, thinner, ultra pure water (DI water for short) and developer. The monitoring method of the embodiment can monitor the hydrophobic impurities in the chemicals and also monitor the hydrophobic impurities in other chemicals used in the photolithography process. In addition, when monitoring hydrophobic impurities of chemicals used in the photolithography process, a single chemical may be monitored, or several different chemicals may be mixed together to monitor, specifically, according to step requirements of different stages of the photolithography process, for example, a developer may be mixed with ultrapure water as a monitoring object, or a single developer or ultrapure water may be used as a monitoring object.
As an example, monitoring hydrophilic impurities in chemicals is included in addition to monitoring hydrophobic impurities in chemicals.
As a specific example, a method of monitoring hydrophilic impurities of a chemical includes: the surface of the bare wafer is coated with the chemicals, and hydrophilic impurities in the chemicals can be effectively adsorbed due to adsorption of water molecules on the surface of the bare wafer; the bare wafer coated with the chemical is then measured using a measuring machine to monitor the hydrophilicity in the chemical. Hydrophilic impurities introduced into the pipeline can also be monitored.
As another specific example, the monitoring of the hydrophilic impurities and the hydrophobic impurities of the chemical may be performed by using the same bare wafer for the second coating, or may be performed by using different bare wafers for the first coating, and the specific monitoring mode may be selected in consideration of the properties of the chemical, the monitoring efficiency and the monitoring cost. For example, considering the chemical properties of photoresist, the hydrophobic impurities and hydrophilic impurities need to be monitored by coating with different bare wafers at a time, that is, one bare wafer is used to monitor the hydrophilic impurities in the chemical, and the other bare wafer is used to monitor the hydrophobic impurities in the chemical. For another example, considering the monitoring cost, the diluent or the developer can be coated for the second time to complete the monitoring of the hydrophobic impurities and the hydrophilic impurities, namely, firstly, the chemical is coated on the surface of the bare wafer, then, the bare wafer coated with the chemical is measured by using a measuring machine to monitor the hydrophilic impurities in the chemical, and finally, the chemical coated on the surface of the bare wafer is cleaned, so that the monitoring of the relativity impurities is realized; next, a layer of hexamethyldisilazane coating is coated on the surface of the bare wafer by using the same bare wafer so as to make the surface of the bare wafer in a hydrophobic state, then a chemical is coated on the surface of the coating, and then the bare wafer coated with the chemical on the coating is measured by using a measuring machine so as to monitor the hydrophobic impurities in the chemical.
As yet another specific example, to achieve accurate measurement, the impurities on the bare wafer and hexamethyldisilazane coating may also be monitored prior to the monitoring of the impurities in the chemical, the specific steps including: after the bare wafer is provided, measuring the bare wafer by using a measuring machine to monitor impurities on the bare wafer to obtain a first impurity value; after the surface of the bare wafer is coated with the hexamethyldisilazane coating, the bare wafer coated with the coating is measured by using a measuring machine to monitor impurities on the bare wafer and the coating, and a second impurity value is obtained; the impurities of the coating are obtained by subtracting the first impurity value from the second impurity value.
The effect of monitoring the hydrophobic impurities in this example will be described below with reference to specific experimental data. As shown in fig. 1, the result of monitoring the impurity on the hexamethyldisilazane coating is shown, wherein the impurity data (pre date) on the 8-piece bare wafer are: 25. 7, 34, 18, 8, 11, 4, 10, i.e. the first impurity value; impurity data (post date) on 8 bare wafers monitored after application of hexamethyldisilazane coating were: 23. 8, 34, 21, 8, 12, 4, 9, i.e., the second impurity value, whereby the hexamethyldisilazane coating is substantially free of impurities. As shown in fig. 2, the results of monitoring hydrophobic impurities in the mixed chemicals of ultrapure water and developer are shown, wherein impurity data (pre date) measured on 6 bare wafers are: 12. 4, 9, 17, 10, 11; impurity data (post date) in the chemicals measured by the monitoring method of hydrophobic impurities of the present embodiment after coating the mixed chemicals of ultrapure water and developer are respectively: 142. 5, 284, the impurity data (post date) of the chemical measured by the detection method of the prior art are: 19. 10, 15; and the impurities in the chemical measured by the method for monitoring hydrophobic impurities of the present example in fig. 2 were monitored by fig. 3, and the results showed that most of the impurities were impurities, and that the hydrophobic impurities containing lead (Pb) were shown in the elemental analysis of fig. 4.
The embodiment also provides a method for manufacturing the semiconductor device, and the method for monitoring the impurities of the photolithography process chemicals is included in the manufacturing process of the semiconductor device.
In summary, the present invention provides a method for monitoring chemical impurities in a photolithography process, wherein a layer of hexamethyldisilazane coating HMDS is coated on the surface of a bare wafer, and the HMDS replaces adhesion between water and an oxide layer on the surface of the bare wafer, so as to form a coating layer which is easy to adsorb hydrophobic substances, so that after the chemical is coated on the coating layer, hydrophobic impurities in the chemical can be effectively adsorbed, and meanwhile, unnecessary elements of other semiconductor products are not introduced in the monitoring process, thereby preventing secondary pollution. The monitoring method can be used for directly monitoring the hydrophobic impurities in the chemicals, and generally the chemicals are purchased, and an upstream manufacturer can provide the purity of the chemicals, so that the monitored hydrophobic impurities can be judged as the hydrophobic impurities introduced into the pipeline when the purchased chemicals are transmitted to a process node through the pipeline, namely the pipeline is reminded of the need of impurity removal. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A method of monitoring impurities in a lithographic process chemistry, comprising: the method of monitoring the impurity of the chemical includes monitoring hydrophobic impurities in the chemical;
the method for monitoring the hydrophobic impurities in the chemical comprises the following steps:
providing a bare wafer;
coating a layer of coating on the surface of the bare wafer, wherein the coating is a hexamethyldisilazane coating so that the surface of the bare wafer is in a hydrophobic state;
coating the surface of the coating with chemicals to be monitored;
the bare wafer coated with the chemical on the coating is measured using a measuring machine to monitor hydrophobic impurities in the chemical.
2. The method of monitoring for impurities of a lithographic process chemical according to claim 1, wherein: the parameters of the hexamethyldisilazane coating are: the pH value is between 8.4 and 8.6, and the density is between 0.7kg/m 3 ~0.8kg/m 3 The concentration is more than 99 percent; the coating speed is 2300 ml/min-2600 ml/min, and the dosage is 1400 ml-160 ml.
3. The method of monitoring for impurities of a lithographic process chemical according to claim 2, wherein: the parameters of the hexamethyldisilazane coating are: pH 8.5, density 0.77kg/m 3 Concentration > 99%; the coating speed was 2500ml/min and the amount was 1500ml.
4. The method of monitoring for impurities of a lithographic process chemical according to claim 1, wherein: the chemicals include at least one of photoresist, thinner, ultrapure water and developer required for the photolithography process.
5. The method of monitoring for impurities of a lithographic process chemical according to claim 1, wherein: the method of monitoring the impurity of the chemical further comprises monitoring the hydrophilic impurity in the chemical.
6. The method of monitoring impurities in a lithographic process chemical according to claim 5, wherein the method of monitoring hydrophilic impurities in the chemical comprises: prior to applying the coating: coating the surface of the bare wafer with the chemical; measuring the bare wafer coated with the chemical by using a measuring machine to monitor hydrophilic impurities in the chemical; and finally, cleaning the chemical coated on the surface of the bare wafer.
7. The method of monitoring for impurities of a lithographic process chemical according to claim 1, wherein: after the bare wafer is provided, measuring the bare wafer by using a measuring machine to monitor impurities on the bare wafer to obtain a first impurity value; after the surface of the bare wafer is coated with the coating, measuring the bare wafer coated with the coating by using a measuring machine to monitor impurities on the bare wafer and the coating so as to obtain a second impurity value; and obtaining the impurity of the coating by subtracting the first impurity value from the second impurity value.
8. The method of monitoring impurities in a lithographic process chemistry according to any one of claims 1 to 7, wherein: the chemical is transported through a pipeline.
9. The method of monitoring for impurities of a lithographic process chemical according to claim 1, wherein: the hydrophobic impurities include lead.
10. A method of manufacturing a semiconductor device, characterized in that the method of manufacturing a semiconductor device comprises the method of monitoring impurities of a photolithography process chemical according to any of claims 1 to 9.
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| JPH049950A (en) * | 1990-04-27 | 1992-01-14 | Dainippon Printing Co Ltd | Photomask and processing method thereof |
| US5888926A (en) * | 1995-08-28 | 1999-03-30 | University Of Cincinnati | Process for forming a sorbent-metal complex by employing a sorbent precursor |
| US6145372A (en) * | 1997-04-30 | 2000-11-14 | Texas Instruments Incorporated | Apparatus and method for detecting impurities in wet chemicals |
| JPH10332554A (en) * | 1997-05-29 | 1998-12-18 | Nippon Steel Corp | Method for measuring surface impurities |
| US7732225B2 (en) * | 2006-06-29 | 2010-06-08 | Texas Instruments Incorporated | Method for measuring contamination in liquids at PPQ levels |
| JP4936186B2 (en) * | 2008-01-07 | 2012-05-23 | 清水建設株式会社 | Surface contamination degree evaluation method and surface contamination degree evaluation apparatus |
| US8143078B2 (en) * | 2009-12-23 | 2012-03-27 | Memc Electronic Materials, Inc. | Methods for monitoring the amount of contamination imparted into semiconductor wafers during wafer processing |
| CN112614789A (en) * | 2020-11-26 | 2021-04-06 | 徐州鑫晶半导体科技有限公司 | Control method for metal impurities on surface of silicon wafer |
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Address after: 510700 No. 28, Fenghuang fifth road, Huangpu District, Guangzhou, Guangdong Patentee after: Yuexin Semiconductor Technology Co.,Ltd. Address before: 510700 No. 28, Fenghuang fifth road, Huangpu District, Guangzhou, Guangdong Patentee before: Guangzhou Yuexin Semiconductor Technology Co.,Ltd. |