Etching residue remover composition

Abstract

The invention provides an etching residue removing agent composition. The composition contains hydroxylamine and derivatives thereof, a surfactant, a metal corrosion inhibitor, an amine pH regulator, nitrogen-containing organic acid and water. The composition is used for cleaning a cobalt layer process with the particle size of 7 nm or above, has good cleaning capacity for polymer residues after photoresistance and plasma ashing, metal oxides and fluorides, has good compatibility for metal materials such as Co and TiN and low-K materials such as SiN, silicon oxide and TEOS, and is large in process operation window and good in application prospect.

Description

Technical Field

[0001] The present invention relates to an etching residue remover composition, and more particularly to a cleaning composition. Background Art

[0002] In the semiconductor manufacturing process, photoresist plays a huge role. A series of patterns can be transferred to the wafer substrate through photoresist, and removing photoresist has become the focus of the semiconductor manufacturing process, which can effectively reduce the impact on subsequent processes. There are two main methods for removing photoresist: dry method and wet method. The wet method is the mainstream, but for some photoresists that are "hardened" after ICP or ion implantation processes, the wet method will not be clean. At the same time, some organic-metal cross-linked products that are difficult to remove will also be produced during the dry photoresist removal process, which increases the difficulty of removing photoresist. In recent years, as the process nodes continue to move towards more advanced manufacturing, the requirements for photoresist removal are getting higher and higher. In particular, Co is used to replace Cu in some layers of processes above 7nm. While removing the photoresist, metals such as Co must also be well protected. A method that can effectively remove plasma etching residues and plasma ashing residues is required, and it must be non-corrosive to all exposed substrate materials, especially Co is non-corrosive for some layers of processes above 7nm.

[0003] CN105849245B mentions at least one chelating agent is added, and the chelating agent is a polyamino polycarboxylic acid. Aminocarboxyl chelating agents are a class of organic compounds with hydrophilicity and chelation, and their molecular structure contains amino and carboxyl groups. Such compounds have good metal ion chelation and coordination, and the metal complex formed by the coordination of aminocarboxyl chelating agents with metal ions can make the metal ions in the solution inactive, preventing metal oxidation and corrosion: aminocarboxyl chelating agents can effectively prevent metal oxidation and corrosion in water, thereby protecting the metal surface. However, aminocarboxyl chelating agents have poor desorption ability on the surface of materials, and the main reasons are as follows: 1. Limitation of molecular structure: carboxyl and amine groups exist simultaneously in the molecular structure of aminocarboxyl chelating agents, making its molecular structure more complicated, and the intermolecular force is strong, resulting in strong adsorption of molecules on the surface of materials, and it is difficult to desorb from the surface. 2. Lack of specific structure: Some surfactants with specific small molecular structures, such as sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS), have good desorption ability on the surface of materials because they have simple molecular structures and are easy to desorb from the surface. 3. Counterion effect: When aminocarboxylic chelating agents and metal ions form complexes, counterion effects will occur, thereby enhancing the interaction between the chelating agent and the surface, making the desorption ability weaker. Therefore, it has a certain impact on the subsequent filling of other materials.

[0004] Therefore, there is a need in the art for a composition for removing residues from cementitious materials that avoids the use of aminocarboxylic chelating agents, which can not only provide excellent removal effects but also reduce corrosion to materials. Summary of the invention

[0005] The invention discloses an etching residue remover composition, which has good cleaning ability for photoresist, polymer residue after plasma ashing, metal oxide, and fluoride, and is used for cleaning of cobalt layer processes above 7nm, and has good compatibility with metals such as Co and TiN and Low-K materials, and has little residual attachment after cleaning, which is beneficial to subsequent operations. The composition has a large process operation window and good application prospects.

[0006] The invention provides an etching residue remover composition, which contains 1) hydroxylamine and its derivatives; 2) surfactant; 3) metal corrosion inhibitor; 4) amine pH regulator; 5) nitrogen-containing organic acid; and 6) water.

[0007] Furthermore, the hydroxylamine and its derivatives are selected from one or more of hydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, acetohydroxamic acid, and o-benzylhydroxylamine.

[0008] Further, the surfactant can be selected from alcohol ether solvents, including ethylene glycol monobutyl ether, ethylene glycol glycidyl ether, poly(ethylene glycol-propylene glycol) monobutyl ether, diethylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, dodecylamine polyoxyethylene ether, polyethylene glycol, polyethylene glycol-propylene glycol copolymer, n-hexanol, 1,2-pentanediol, 1,2-propylene glycol, 1,3-propylene glycol, benzyl alcohol, dioxane, ethanol, n-propanol, isopropanol, and n-butanol; it can also be selected from non-ionic surfactants, including SUPERWET-320, SUPERWET-340, SUPERWET-360, SURFYNOL420, SURFYNOL440, and coconut fatty acid diethanolamide. It can also be selected from cationic surfactants, including dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, benzalkonium chloride, dodecylbenzyldimethylammonium chloride, hexadecyltrimethylammonium bromide, tetraheptylammonium bromide.

[0009] Further, the metal corrosion inhibitor is selected from one or more of pyrazole, 1-methylpyrazole, 3,5-dimethylpyrazole, pyrazine, benzotriazole, methylbenzotriazole, 1H-benzotriazole methanol, 1,2,4-triazole-3-carboxylic acid methyl ester, 5-benzyl-1H-tetrazole, 1-phenyl-5-mercaptotetrazole, 5-benzylthio-1H-tetrazole, 5-methyltetrazole, 2-mercaptothiadiazole, methimazole, mercaptoimidazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.

[0010] Furthermore, the amine pH regulator is selected from one or more of diglycolamine, ethanolamine, ethylenediamine, diethanolamine, diethylenetriamine, triethylenetetramine, hydroxyethylethylenediamine, N-methylethanolamine, n-propanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, and triethylenetetramine.

[0011] Further, the nitrogen-containing organic acid is selected as a polycarboxylic acid containing one nitrogen atom. Further, the polycarboxylic acid containing one nitrogen atom is selected from one or more of iminodiacetic acid, iminodipropionic acid, iminodisuccinic acid, N-(2-acetylamino)iminodiacetic acid, N-(phosphonomethyl)iminodiacetic acid, nitrilotriacetic acid, glutamic acid, and aspartic acid.

[0012] Furthermore, the mass percentage of the hydroxylamine and its derivatives is 0.1%-10%, preferably 0.5%-10%.

[0013] Furthermore, the mass percentage of the surfactant is 0.001%-10%, preferably 0.001%-5%.

[0014] Furthermore, the mass percentage of the metal corrosion inhibitor is 0.01%-3%.

[0015] Furthermore, the mass percentage of the amine pH regulator is 0.01%-5%.

[0016] Furthermore, the pH value of the composition is in the range of 7-10, preferably in the range of 8-9.

[0017] Furthermore, the mass percentage of the nitrogen-containing organic acid is 0.01%-5%.

[0018] All reagents in this application are commercially available.

[0019] Compared with the prior art, the advantages of the present invention are:

[0020] Provided is an etching residue remover composition, which has good photoresist removal capability and does not contain aminocarboxylic chelating agents, is used for cleaning of cobalt layers above 7nm, has good cleaning capability for polymer residues, metal oxides, and fluorides after plasma ashing, and has good compatibility with TiN and Low-K materials, a large process operation window, and good application prospects. The technical problem that aminocarboxylic chelating agents have poor desorption capability on the surface of materials and have a certain impact on subsequent filling of other materials is solved. DETAILED DESCRIPTION

[0021] The advantages of the present invention are described in detail below in conjunction with specific embodiments.

[0022] The cleaning liquid composition according to the present invention is described in detail below by examples and test results, but is not limited to these examples and the results shown in each test. The cleaning liquid composition of the present invention can be embodied in a variety of specific formulations, wherein the specific components of the composition are discussed in terms of weight percentage for all such cleaning liquid compositions.

[0023] Preparation method: According to the formulations (specific components and their corresponding specific contents) of the embodiments and comparative examples in Table 1 below, the components are simply mixed.

[0024] Table 1 Some embodiments of the present invention

[0025]

[0026]

[0027] The units of the above contents are all mass percentage.

[0028] In order to investigate the compatibility of the composition with various materials, the etching rates of metal Co, TiN, non-metal silicon oxide and SiN were further tested.

[0029] The metal etching rate test method is as follows: Co and TiN blank wafers are selected, the blank wafers are sliced ​​into 5*5cm size, and placed in a single-wafer rotary cleaning machine for treatment. The treatment time range is 3-20min, preferably 10min, the rotation speed setting range is 200-900rpm, preferably 600rpm, and the test temperature is 25-70℃, preferably 50℃. After treatment, take out, rinse, and blow dry with high-purity nitrogen.

[0030] The corrosion rate test method is as follows:

[0031] 1) Use a metal film thickness gauge to test the resistance (R1) of a 5*5cm metal blank wafer to be tested;

[0032] 2) placing the 5*5 cm metal blank wafer to be tested in a single wafer spin cleaning machine;

[0033] 3) Take out the 5*5cm metal blank wafer, wash it with deionized water, blow dry it with high-purity nitrogen, and then use a metal film thickness gauge to test the resistance (R2) of the metal blank wafer;

[0034] 4) By inputting the above resistance value change and processing time into a suitable program, the etching rate can be calculated. The calculation formula is as follows:

[0035] ER=K(R2-R1) / T

[0036] Among them, R1 and R2 are the resistance values ​​of the metal blank wafer; T is the processing time of the microcontroller; K value is the coefficient, and the K value of different metal materials is different. The unit of metal corrosion rate is

[0037] The etch rate test method for non-metallic materials (SiN, silicon oxide) is as follows:

[0038] 1) Using an ellipsometer to measure the first thickness D1 of the non-metal material layer (AlN) of a 5*5cm non-metal blank wafer to be tested;

[0039] 2) placing the 5*5 cm non-metallic blank wafer to be tested in a single-wafer spin cleaning machine for 3 to 20 minutes, with the rotation speed set at 200 to 900 rpm;

[0040] 3) taking out the blank wafer, washing it with deionized water, drying it with high-purity nitrogen gas, and then measuring the second thickness D2 with an ellipsometer;

[0041] 4) By inputting the above thickness changes and processing time into a suitable program, the corrosion rate can be calculated. The calculation formula is as follows:

[0042] ER=(D1-D2) / T

[0043] Wherein, D1 and D2 are the first thickness and the second thickness of the non-metal blank wafer respectively; T is the processing time.

[0044] The measured etching rates are shown in Table 2.

[0045] Table 2 Etching rate of blank wafer by compositions of Examples 1-13 of the present invention

[0046]

[0047]

[0048] From the results in Table 2, it can be seen that within the operating window of operating temperature of 25-70°C, rotating speed of 200-900 rpm and operating time of 3-20 min, the etching rates of Co, TiN, silicon oxide and SiN are relatively low. The composition has good compatibility with the above four materials at different temperatures, rotating speeds and operating times.

[0049] Table 3 Some examples and comparative examples of the present invention

[0050]

[0051] In order to investigate the residual organic matter of the composition after treating the wafer surface, the present invention selected Examples 14 and 15 and Comparative Examples 4 and 5 in Table 3 for testing, and adopted the following technical means: Co blank wafers were selected, sliced ​​into 5*5cm size, placed in a single-wafer rotary cleaning machine for processing, the processing time was selected to be 3min, the rotation speed was set to be 600rpm, and the test temperature was selected to be 40°C. After the processing, the wafers were taken out and rinsed on a single-chip computer, the processing time was selected to be 30s, the rotation speed was set to be 600rpm, and the rinse temperature was selected to be 25°C. Finally, they were blown dry with high-purity nitrogen, and the element abundance of C, N, O, and Co on the wafer surface was tested by XPS. The test results are shown in Table 4.

[0052] Table 4 XPS results of Co wafer surface after treatment

[0053] Example C 1s N 1s O 1s 2p 14 43.81 3.26 29.02 23.91 15 44.03 3.79 29.23 22.95 Contrast 4 47.80 6.51 29.66 16.03 Contrast 5 45.21 9.46 28.69 16.64

[0054] As can be seen from Table 4, after the Co surface is treated with the composition example, the Co abundance is higher and the N and C abundances are lower, indicating that the amount of residual organic matter in the system is lower than that in the comparative example system, which is beneficial for subsequent operations on the Co layer, such as filling W or other metals into related structures.

[0055] Table 5 Test results of Co ion content (ppb) in some examples

[0056] Example CoO treatment results CoF2 treatment results 14 36.21 1003.36 15 40.39 1414.22 DIW 1.56 6.03

[0057] Table 5 shows the solubility of CoF2 and CoO in some embodiments, and the blank is deionized water. The test method adopted by the present invention is: take an equal amount of CoF2 / CoO and dissolve it in 1L of the composition solution or water respectively, and test the Co ion concentration by ICP-MS after stabilization. It can be seen that the solubility of the composition of the present invention for CoF2 / CoO is much greater than that of deionized water, indicating that the composition can effectively remove the fluoride and oxide of cobalt on the side wall or top after plasma treatment.

[0058] In summary, the positive progress of the present invention is that: the present invention discloses an etching residue remover composition, and does not contain aminocarboxylic chelating agents, has good cleaning ability for photoresist, polymer residues after plasma ashing, metal oxides, and fluorides, and is used for cleaning of cobalt layer processes above 7nm, and has good compatibility with metals such as Co and TiN and Low-K materials, and has few residual attachments after cleaning, which is beneficial to subsequent operations. The composition has a large process operation window and good application prospects.

[0059] The specific embodiments of the present invention are described in detail above, but they are only examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions made to the present invention are also within the scope of the present invention. Therefore, the equalization changes and modifications made without departing from the spirit and scope of the present invention should be included in the scope of the present invention.

Claims

1. An etching residue remover composition, characterized in that include: 1) Hydroxylamine and its derivatives; 2) Surfactants; 3) Metal corrosion inhibitors; 4) Amine pH regulator; 5) Nitrogen-containing organic acid; 6) Water.

2. The composition according to claim 1, characterized in that The hydroxylamine and its derivatives are selected from one or more of hydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, acetohydroxamic acid, and o-benzylhydroxylamine.

3. The composition according to claim 1, characterized in that The mass percentage of the hydroxylamine and its derivatives is 0.1%-10%.

4. The composition according to claim 1, characterized in that The mass percentage of the hydroxylamine and its derivatives is 0.5%-10%.

5. The composition according to claim 1, characterized in that The surfactant is selected from alcohol ether solvents, including: ethylene glycol monobutyl ether, ethylene glycol glycidyl ether, poly (ethylene glycol-propylene glycol) monobutyl ether, diethylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, dodecylamine polyoxyethylene ether, polyethylene glycol, polyethylene glycol-propylene glycol copolymer, n-hexanol, 1,2-pentanediol, 1,2-propylene glycol, 1,3-propylene glycol, benzyl alcohol, dioxane, ethanol, n-propanol, isopropanol, n-butanol or one or more thereof.

6. The composition according to claim 1, characterized in that The surfactant is selected from nonionic surfactants, including: one or more of SUPERWET-320, SUPERWET-340, SUPERWET-360, SURFYNOL420, SURFYNOL440, and coconut fatty acid diethanolamide.

7. The composition of claim 1, characterized in that The surfactant is selected from cationic surfactants, including: one or more of dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, benzalkonium chloride, dodecylbenzyldimethylammonium chloride, hexadecyltrimethylammonium bromide, tetraheptylammonium bromide.

8. The composition of claim 1, characterized in that The mass percentage of the surfactant is 0.001%-10%.

9. The composition according to claim 1, characterized in that The mass percentage of the surfactant is 0.001%-5%.

10. The composition of claim 1, characterized in that The metal corrosion inhibitor is selected from one or more of pyrazole, 1-methylpyrazole, 3,5-dimethylpyrazole, pyrazine, benzotriazole, methylbenzotriazole, 1H-benzotriazole methanol, 1,2,4-triazole-3-carboxylic acid methyl ester, 5-benzyl-1H-tetrazole, 1-phenyl-5-mercaptotetrazole, 5-benzylthio-1H-tetrazole, 5-methyltetrazole, 2-mercaptothiadiazole, methimazole, mercaptoimidazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.

11. The composition of claim 1, characterized in that The mass percentage of the metal corrosion inhibitor is 0.01%-3%.

12. The composition of claim 1, characterized in that The amine pH regulator is selected from one or more of diglycolamine, ethanolamine, ethylenediamine, diethanolamine, diethylenetriamine, triethylenetetramine, hydroxyethylethylenediamine, N-methylethanolamine, n-propanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, and triethylenetetramine.

13. The composition of claim 1, characterized in that The mass percentage of the amine pH regulator is 0.01%-5%.

14. The composition of claim 1, characterized in that The adjustment range of the amine pH regulator is 7-10.

15. The composition of claim 1, characterized in that The adjustment range of the amine pH regulator is 8-9.

16. The composition of claim 1, characterized in that The nitrogen-containing organic acid is selected from polycarboxylic acids containing one nitrogen atom.

17. The composition according to claim 16, characterized in that The polycarboxylic acid containing one nitrogen atom is selected from one or more of iminodiacetic acid, iminodipropionic acid, iminodisuccinic acid, N-(2-acetylamino)iminodiacetic acid, N-(phosphonomethyl)iminodiacetic acid, nitrilotriacetic acid, glutamic acid, and aspartic acid.

18. The composition of claim 1, characterized in that The mass percentage of the nitrogen-containing organic acid is 0.01%-5%.

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