CN119028819B - Method for removing cementing agent in device at low temperature - Google Patents
Method for removing cementing agent in device at low temperature Download PDFInfo
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Abstract
本发明提供一种低温去除器件中胶结物的方法，涉及半导体技术领域，所述方法包括：在第一温度下，通入清洗气体进行等离子体处理，以去除器件中的胶结物；其中，所述第一温度为≤65℃；所述清洗气体包含有氟基气体；所述清洗气体中氟基气体的体积占比为5~10‰；所述清洗气体还包含有氧气和/或氮气。本发明能够在低温下实现器件的通孔周围胶结物的有效去除，并且不会对器件产生负面影响，应用前景广阔。
The present invention provides a method for removing cement in a device at low temperature, which relates to the field of semiconductor technology. The method comprises: introducing a cleaning gas at a first temperature for plasma treatment to remove cement in the device; wherein the first temperature is ≤65°C; the cleaning gas contains a fluorine-based gas; the volume proportion of the fluorine-based gas in the cleaning gas is 5-10‰; the cleaning gas also contains oxygen and/or nitrogen. The present invention can effectively remove cement around the through hole of the device at low temperature, and will not have a negative impact on the device, and has broad application prospects.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a method for removing cementing agent in a device at a low temperature.
Background
The semiconductor photoresist removing process is generally divided into two types, wet photoresist removing and dry photoresist removing. Compared with wet photoresist removal, the plasma dry photoresist removal utilizes high-energy plasma to treat the photoresist surface, has thorough and rapid photoresist removal, does not need to introduce chemical substances, reduces the corrosion and damage to wafer materials, and is the best mode in the existing photoresist removal process. The working principle is that the wafer product is placed in a vacuum reaction system, a small amount of oxygen and nitrogen are introduced, high voltage and high power are added, a high-frequency signal is generated by a high-frequency signal generator, an induction electromagnetic field is generated in the vacuum system, the oxygen is ionized, and a mixture of oxygen ions, activated oxygen atoms, oxygen molecules, electrons and the like is formed. The activated oxygen (reactive atomic oxygen) can rapidly oxidize the photoresist into a volatile gas that is pumped away by a mechanical pump.
Because the high-temperature photoresist removal can damage certain etching film quality, a low-temperature plasma surface photoresist removal process is introduced, but the photoresist removal activity can be lowered due to the reduction of temperature, and the phenomenon that certain components are not removed cleanly exists, so that unnecessary residues influence the process.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for removing cementing materials in a device at low temperature, which can remove cementing materials around a through hole at low temperature by introducing fluorine-based gas, particularly CF 4, into gas treated by plasma, thereby improving the product quality of the final device and having wide application prospect.
It should be noted that, in the present back end through hole etching structure behind the chip, the through hole is more difficult to remove than the cement remained in or around the through hole, on one hand, the performance of the through hole needs to be ensured not to be affected, on the other hand, the effective removal of the cement inside the through hole needs to be realized, and the through hole has higher difficulty in removing the cement due to the limitation of the aperture itself, so the invention develops the method for removing the cement in the low-temperature device.
To achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a method for cryogenically removing cement in a device, said method comprising:
Introducing cleaning gas at a first temperature to perform plasma treatment so as to remove cementing matters in the device;
wherein the first temperature is less than or equal to 65 ℃, and the cleaning gas contains fluorine-based gas.
It should be noted that, in general, the process of removing the binder is above 70 ℃, and at such high temperature, damage to the etched film quality is easily caused, for example, when the material is LN and/or LT. The invention adopts a low-temperature etching process, however, due to the specificity of the device, the effective removal of the cementing agent is difficult to realize at low temperature, and through multi-side research, the invention discovers that the removal of the cementing agent can be effectively realized by adopting the cleaning gas containing fluorine-based gas, and the device is not negatively influenced.
Specifically, the first temperature is equal to or less than 65 ℃, and may be, for example, 10 ℃,12 ℃,15 ℃,21 ℃, 27 ℃, 32 ℃, 38 ℃, 43 ℃, 49 ℃, 54 ℃, 60 ℃, 65 ℃, or the like.
Preferably, the fluorine-based gas includes CF 4.
The preferred fluorine-based gas of the present invention is CF 4, which has the advantage of greater capability of CF 4 in removing silicon than other fluorine-containing gases such as CH 2F2、CH3F、CHF3、C2H3F3, and the use of gases such as CH 2F2 not only has relatively less capability of removing silicon, but also has heavier deposits.
Preferably, the volume ratio of the fluorine-based gas in the cleaning gas is 5-10%, for example, 5%, 5.5%, 5.8%, 5.6%, 6.0%, 6.5%, 6.8%, 7.0%, 7.4%, 7.5%, 8.0%, 8.3%, 8.5%, 9.0%, 9.2%, or 10%.
In the present invention, the volume ratio of the fluorine-based gas is preferably controlled within the above range, and when the volume ratio of the fluorine-based gas is large, there is a case where the device is adversely affected, and when the volume ratio of the fluorine-based gas is small, there is a case where the removal of the silica residue is incomplete.
Preferably, the purge gas further comprises oxygen and/or nitrogen.
Preferably, the volume ratio of oxygen to nitrogen in the purge gas is 4-10:1, for example, 4:1, 4.7:1, 5.4:1, 6:1, 6.7:1, 7.4:1, 8:1, 8.7:1, 9.4:1, or 10:1, etc.
And/or the flow rate of the cleaning gas is 5000-10000 sccm, for example, 5000sccm, 6660sccm, 8330sccm, 10000sccm, etc.
Preferably, the first temperature is 15 to 65 ℃, for example, 15 to 20 ℃, 25 ℃, 28 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 65 ℃ or the like, and preferably 15 to 30 ℃.
The temperature in the invention can be further reduced to 15-30 ℃, the device is hardly affected, and the cementing agent in the device can be effectively removed.
Preferably, the bias power of the plasma treatment is 100 W.ltoreq.U.ltoreq.250W, and for example, the bias power may be 250W, 245W, 240W, 230W, 220W, 200W, 180W, 170W, 160W, 150W, 140W, 130W, 120W, 110W, 100W or the like.
It should be noted that another core invention is that the bias power setting during plasma processing is critical, since not only is the cement removal required to be considered during the cement removal process, but also the device is not damaged or negatively affected during this process. The bias power of plasma treatment needs to be strictly controlled within the range after fluorine-based gas is introduced, otherwise, the situation that byproducts are generated by reaction with the silicon nitride film layer easily occurs, and meanwhile, the silicon nitride film layer is damaged, so that the performance of a device is influenced.
The other parameters of the plasma treatment are not particularly limited, and may be performed by using process parameters well known to those skilled in the art, or may be adjusted according to practical situations.
For example, the power of the plasma treatment is 2000 to 2500W, and may be 2000W, 2050W, 2100W, 2150W, 2200W, 2250W, 2300W, 2350W, 2400W, 2450W, 2500W, or the like.
Preferably, the device comprises a stacked arrangement of film layers and via layers.
The film layer is made of a nitrogen-containing layer, preferably a silicon nitride layer.
The device of the present invention may be, for example, a back-end via etch structure behind a chip.
Preferably, the thickness of the film layer is 100 to 300nm, for example, 100nm, 120nm, 130nm, 140nm, 150nm, 180nm, 200nm, 220nm, 230nm, 250nm, 280nm or 300nm may be used.
Preferably, the thickness of the through hole layer is 10 to 30nm, for example, 10nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 22nm, 23nm, 24nm, 27nm, 30nm, or the like may be used.
Preferably, the through hole layer is provided with a through hole, and the periphery of the through hole is provided with cementing agent.
Preferably, the material of the through hole layer is silicon-containing compound, preferably silicon oxide.
Preferably, the diameter of the through hole is 50-1000 nm, for example, 50nm, 150nm, 260nm, 360nm, 470nm, 570nm, 680nm, 780nm, 890nm or 1000nm may be used.
Preferably, the depth of the through hole is 50-500 nm, for example, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm may be used.
The diameter and depth of the through holes in the invention also essentially bring great difficulty to the removal of the cementing agent, and the removal of the cementing agent remained in the through holes is completely incomparable with the removal of the cementing agent in the flat layer due to the small diameter and deep depth of the through holes. In this way, the invention comprehensively adopts low temperature and the cleaning gas containing fluorine-based gas for removal, which can not only not affect the diameter and depth of the through hole, but also realize the effective removal of the cementing agent.
Preferably, the cross section of the through hole is inverted T-shaped, wherein the acute angle of the inclined edge of the inverted T-shaped and the bottom is 75-90 degrees, for example, 75 degrees, 78 degrees, 79 degrees, 80 degrees, 82 degrees, 84 degrees, 85 degrees, 86 degrees, 87 degrees, 88 degrees, 90 degrees or the like.
Preferably, the material of the cement comprises photoresist.
The invention has no special requirement on the material of the photoresist, can adopt the photoresist material well known to the person skilled in the art, can be adjusted according to the actual situation, and generally comprises three main components of photosensitive resin, sensitizer and solvent.
The materials of the photosensitive resin, the sensitizer and the solvent in the invention are not particularly required, and photoresist materials well known to those skilled in the art can be adopted, and can be adjusted according to practical situations, wherein the photosensitive resin can be polymethacrylate, polyimide or the like, the sensitizer can be aromatic aldehyde, ketone or the like, and the solvent can be any one or a combination of at least two of acetone, ethanol, isopropanol, butanone or the like.
Preferably, the cement contains silica slag.
The invention effectively removes the cementing agent in the through hole by adopting a method of fluorine-containing gas at low temperature, which is just because the cementing agent contains silicon slag and the cementing agent remains in the through hole, so that the cementing agent in the device is difficult to effectively remove by using conventional cleaning gas, and the main silicon slag can be removed only at high temperature, and the etching film is easily damaged at high temperature.
Preferably, the source of the silicon residue includes silicon residue generated when etching through silicon oxide vias remaining on the surface of the cement.
Compared with the prior art, the invention has at least the following beneficial effects:
The method for removing the cementing agent in the device at low temperature can remove the cementing agent around the hole of the device at low temperature, does not damage the device, has lower energy consumption, and solves the problem that the etching film quality is damaged by the removing glue at the existing high temperature.
Drawings
FIG. 1 is a pattern of through holes in the device after cement removal in example 1 of the present invention.
Fig. 2 is an enlarged schematic view of the single via in fig. 1.
Fig. 3 is a schematic cross-sectional view of the via of fig. 2.
FIG. 4 is a pattern of through holes in the device after cement removal in example 4 of the present invention.
Fig. 5 is an enlarged schematic view of the single via of fig. 4.
Fig. 6 is a schematic cross-sectional view of the via of fig. 5.
FIG. 7 is a pattern of through holes in the device of comparative example 1 after cement removal according to the present invention.
Fig. 8 is an enlarged schematic view of the single via in fig. 7.
Fig. 9 is a schematic cross-sectional view of the via of fig. 8.
Fig. 10 is a schematic view of a device to be cement removed, as directed to an embodiment of the present invention.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
For ease of experimentation, the following examples and comparative examples are directed to a device requiring cement removal that is prepared by the process comprising the steps of:
a photoresist layer is provided on the surface of the device (the silicon oxide layer and the silicon nitride layer which are stacked, a desired photoresist pattern is obtained by exposure and development, a through hole is formed in the silicon oxide layer by etching transferred to the silicon oxide layer (a device diagram having a through hole is shown in fig. 10), and finally, the photoresist layer is removed.
Example 1
The embodiment provides a method for removing cement in a device at a low temperature, wherein the device to be removed of cement comprises a silicon oxide layer and a silicon nitride layer which are stacked.
The thickness of the silicon oxide layer is 200nm, the thickness of the silicon nitride layer is 20nm, the silicon oxide layer is a through hole layer, the through hole layer is provided with a through hole, and the periphery of the through hole is provided with a cementing agent.
The material of the cementing material is photoresist (TOK 20A), the cementing material contains silicon slag, the sources of the silicon slag comprise silicon slag which is generated when silicon oxide through holes are etched and remains on the surface of the cementing material, the diameter of the through holes in the silicon oxide layer is 470nm, the depth of the through holes is 216nm, the cross section of the through holes is of an inverted T shape, and the acute angle range of the inclined edges of the inverted T shape and the bottom is 81.4 degrees.
The method comprises the following steps:
At 25 ℃, a cleaning gas (oxygen: nitrogen=6000 sccm:1000sccm, cf 4 volume per mill) was introduced to perform a plasma treatment to remove cement from the device, wherein the bias power of the plasma treatment was 250W, the power was 2500W, and the pressure was 740mT.
Example 2
The embodiment provides a method for removing cement in a device at a low temperature, wherein the device to be removed of cement comprises a silicon oxide layer and a silicon nitride layer which are stacked.
The thickness of the silicon oxide layer is 300nm, the thickness of the silicon nitride layer is 30nm, the silicon oxide layer is a through hole layer, the through hole layer is provided with a through hole, and the periphery of the through hole is provided with a cementing agent.
The material of the cementing material is photoresist (KMPR 101), the cementing material contains silicon slag, the sources of the silicon slag comprise silicon slag which is generated when silicon oxide through holes are etched, the silicon slag is remained in the cementing material, the diameter of the through holes in the silicon oxide layer is 500nm, the depth of the through holes is 320nm, the cross section of the through holes is of an inverted T shape, and the acute angle range of the inclined edges of the inverted T shape and the bottom is 85.2 degrees.
The method comprises the following steps:
At 15 ℃, a cleaning gas (oxygen: nitrogen=7000 sccm:1000sccm, CF 4 volume fraction 7%o) was introduced for plasma treatment to remove cement from the device, wherein the bias power of the plasma treatment was 250W, the power was 2000W, and the pressure was 730mT.
Example 3
The embodiment provides a method for removing cement in a device at a low temperature, wherein the device to be removed of cement comprises a silicon oxide layer and a silicon nitride layer which are stacked.
The thickness of the silicon oxide layer is 110nm, the thickness of the silicon nitride layer is 20nm, the silicon oxide layer is a through hole layer, the through hole layer is provided with a through hole, and the periphery of the through hole is provided with a cementing agent.
The material of the cementing material is photoresist (TOK 50A), the cementing material contains silicon slag, the sources of the silicon slag comprise silicon slag which is generated when silicon oxide through holes are etched, the silicon slag remains in the cementing material, the diameter of the through holes in the silicon oxide layer is 300nm, the depth of the through holes is 125nm, the cross section of the through holes is of an inverted T shape, and the acute angle range of the inclined edges of the inverted T shape and the bottom is 79.6 degrees.
The method comprises the following steps:
At 30 ℃, a cleaning gas (oxygen: nitrogen=4000 sccm:1000sccm, cf 4 volume fraction 10%o) was introduced to perform a plasma treatment to remove cement from the device, wherein the bias power of the plasma treatment was 100W, the power was 2400W, and the pressure was 740mT.
Example 4
The embodiment provides a method for removing cement in a device at a low temperature, which is the same as that of embodiment 1 except that the bias power is 300W, and will not be described here again.
Example 5
The embodiment provides a method for removing cement in a device at low temperature, which is the same as that in embodiment 1 except that CF 4 is replaced with CH 2F2, and will not be described here again.
Example 6
The embodiment provides a method for removing cement in a device at low temperature, which is the same as that of embodiment 1 except that CF 4 is replaced with C 2H3F3, and will not be described here again.
Example 7
This embodiment provides a method for removing cement from a device, which is the same as embodiment 1 except that no oxygen is included, and will not be described here.
Example 8
This example provides a method for removing cement from a device, which is the same as example 1 except that no nitrogen is included, and will not be described in detail herein.
Comparative example 1
This comparative example provides a method of removing cement from a device, which is the same as example 1, except that it does not contain CF 4, and is not described in detail herein.
Comparative example 2
This comparative example provides a method of removing cement from a device that is identical to comparative example 1 except that the temperature is replaced with 70 ℃, and will not be described in detail herein.
Comparative example 3
This comparative example provides a method of removing cement from a device that is identical to example 1 except that the temperature is replaced with 70 ℃, and will not be described in detail herein.
Comparative example 4
This comparative example provides a method for removing cement from a device at low temperature, which is the same as example 1 except that CF 4 is 15% by volume, and will not be described again.
Comparative example 5
This comparative example provides a method for removing cement from a device at low temperature, which is the same as example 1 except that CF 4 is 1% by volume, and will not be described in detail herein.
TEM test was used to observe the removal of cement from the vias and its impact on the device.
The through hole patterns after the cement removal in the embodiment 1 are shown in fig. 1 to 3, respectively, and it can be seen from fig. 1 to 3 that the cement is completely removed in the embodiment without negative effects on the through hole and the device.
The through hole patterns after removing the cement in example 4 are shown in fig. 4 to 6, respectively, and it can be seen from fig. 4 to 6 that the cement is completely removed in this example, but impurity byproducts are generated in the through hole, and the byproducts are silica residues.
The through hole patterns after the cement is removed in the comparative example 1 are shown in fig. 7-9, and as can be seen from fig. 7-9, the cement is completely removed in the comparative example, and more silica residues still remain on the surface.
The test results of the above examples and comparative examples are summarized in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) According to the comprehensive examples 1-3, the method for removing the cementing agent in the device at the low temperature can effectively remove the cementing agent in the through hole at the temperature of less than or equal to 65 ℃, does not damage the performance of the device, and does not generate impurity byproducts in the through hole;
(2) As can be seen from the combination of examples 1 and 4, in example 1, the bias power was 250W, compared to example 4, in which the cement around the through hole was removed cleanly, no impurity by-product was generated in the through hole, whereas in example 4, the cement around the through hole was removed cleanly, but impurity by-product was generated around the through hole, which adversely affected the performance of the device, thus indicating that the bias power is preferably set within a reasonable range, and the device performance can be ensured while the cement was removed;
(3) As can be seen from the comprehensive examples 1 and comparative examples 4 to 5, in example 1, the volume ratio of CF 4 is 5%o, compared with the volume ratio of CF 4 in comparative examples 4 to 5, which is 15%o and 1%o respectively, in example 1, the cement around the through hole is removed completely, no impurity byproduct is generated in the through hole, the volume ratio of CF 4 in comparative example 4 is higher, the lower silicon nitride layer is damaged, the impurity byproduct is generated in the through hole, and in comparative example 5, the silicon slag is difficult to remove cleanly due to the lower volume ratio of CF 4, and silicon slag remains, therefore, the invention is shown that the preferred setting of the volume ratio of CF 4 in a reasonable range can ensure the device performance while removing the cement;
(4) By combining the embodiment 1 and the embodiment 5-6, the embodiment 5-6 adopts CH 2F2 and C 2H3F3, the embodiment 5-6 has the conditions that silicon slag is seriously remained and sediment is too heavy to influence the photoresist stripping efficiency, and therefore, the invention has the advantages of higher photoresist stripping efficiency and being beneficial to guaranteeing the performance of devices by preferentially adopting CF 4 to remove the cementing material;
(5) It can be seen from the combination of examples 1 and 7-8 that the absence of oxygen in example 7 results in a decrease in the photoresist removing efficiency, and in the same treatment time, the cement remains seriously, and the time of the plasma treatment is prolonged to remove the cement cleanly, but the time of the plasma treatment is long to damage the device, and the absence of nitrogen in example 8 results in a serious decrease in the photoresist removing efficiency, and in the same treatment time, the cement remains seriously, and the cement can be removed cleanly after the time of the plasma treatment is prolonged, but the time of the plasma treatment is long to damage the device, so that the invention is characterized in that the oxygen and the nitrogen are preferably added into the cleaning gas, the cement removing effect is better, and the device performance is more effectively ensured;
(6) As can be seen from the combination of example 1 and comparative examples 1 to 3, comparative example 1 does not contain CF 4, the silicon slag is completely remained and is difficult to completely remove at the low temperature, and comparative examples 2 to 3 use 70 ℃ high temperature condition to cause damage to devices, and impurity byproducts exist in through holes, so that the invention adopts fluorine-based gas and cleans at the low temperature, thereby removing the cementing agent and the silicon slag and preventing the devices from being damaged.
The present invention is described in detail by the above embodiments, but the present invention is not limited to the above detailed features, that is, it does not mean that the present invention must be implemented depending on the above detailed features. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for selected features of the present invention, addition of auxiliary features, selection of specific modes, etc. fall within the scope of the invention and the disclosure.
Claims (8)
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| US6693043B1 (en) * | 2002-09-20 | 2004-02-17 | Novellus Systems, Inc. | Method for removing photoresist from low-k films in a downstream plasma system |
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| CN100377314C (en) * | 2005-12-02 | 2008-03-26 | 北京北方微电子基地设备工艺研究中心有限责任公司 | A method for removing residual polymer in polysilicon etching process |
| JP5933375B2 (en) * | 2011-09-14 | 2016-06-08 | 株式会社日立国際電気 | Cleaning method, semiconductor device manufacturing method, substrate processing apparatus, and program |
| CN103092009B (en) * | 2011-11-08 | 2015-05-20 | 无锡华润华晶微电子有限公司 | Removing method of photoresist used as masking layer of plasma injection |
| CN105824202B (en) * | 2016-05-11 | 2019-10-25 | 上海华虹宏力半导体制造有限公司 | Photoresist removal method and semiconductor device manufacturing method |
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