A low-corrosion, low-residue semiconductor cleaning solution, a preparation method and uses thereof

Abstract

The present application relates to a kind of low residue, low corrosion semiconductor cleaning solution, the cleaning solution includes ultra-pure water 80-90 parts by mass, hexafluorophosphate 3-8 parts, organic alkali 10-30 parts, chelating agent 0.1-2 parts and two-component corrosion inhibitor 0.1-1 part, the two-component corrosion inhibitor includes A agent and B agent, A agent is at least one in adenosine, guanosine, B agent is at least one in polyethylene glycol diamine and dimercapto polyethylene glycol.The cleaning solution especially by the use of two-component corrosion inhibitor, can obtain excellent low residue and low metal corrosion performance, and cleaning is simple, in the field of semiconductor cleaning has excellent technical effect and application prospect.

Description

Technical Field

[0001] This invention relates to a cleaning fluid, its preparation method, and its uses in the field of semiconductor cleaning, and more particularly to a low-corrosion, low-residue semiconductor cleaning fluid, its preparation method, and its uses, belonging to the field of novel cleaning fluid technology in the semiconductor industry. Background Technology

[0002] In semiconductor fabrication, especially in back-to-office (BEOL) processing, patterning such as trenches and vias is achieved through dry etching of dielectric materials using fluorine-based plasma. However, dry etching has several drawbacks. For example, to ensure anisotropy in etching, deposition and etching must occur simultaneously, and the deposited fluorocarbons often need to possess a certain degree of corrosion resistance to promote etching depth. Furthermore, before subsequent metallization, the polymer on the dielectric sidewalls must be completely removed to ensure good adhesion between the metal film and the dielectric material and to prevent voids at the interface. Therefore, thorough cleaning is required after etching to completely remove residues, and the etching process must have low corrosivity to the dielectric material to prevent feature size enlargement.

[0003] However, as technology advances to more advanced stages, interconnect metal lines become increasingly thinner, reducing the acceptable loss during the cleaning phase. Current conventional cleaning solutions contain etchants such as hydrofluoric acid and alkalis, which can cause strong chemical corrosion to metal materials, potentially leading to excessive roughness or wire breakage. Furthermore, the different reactivity of copper (Cu) and the backing layer (Co) also poses a risk of galvanic corrosion.

[0004] Meanwhile, certain components in the cleaning solution, especially the organic protective agents for metals, can cause adhesion problems or electrical performance issues in subsequent coatings if they remain on the metal material. Therefore, the process requires that all components in the cleaning solution be removed as much as possible during the water rinsing stage, ideally completely. However, some commonly used nitrogen-containing heterocyclic azole corrosion inhibitors, such as benzotriazole (BTA), while offering excellent protection for metal materials, can also lead to problems such as organic residues due to their strong adhesion to copper.

[0005] For example, CN116254159A discloses a semiconductor cleaning solution with low corrosivity to cobalt, which uses benzotriazole (BTA) as a corrosion inhibitor for metallic cobalt. However, the XPS spectrum of the cobalt surface after cleaning still shows a strong N absorption signal, indicating that a large amount of BTA residue exists.

[0006] In view of this, the current industry demand is to develop cleaning solutions that have extremely low corrosion to metals, can effectively inhibit galvanic corrosion between contacting metals, and are easy to rinse and leave no organic residue.

[0007] Based on this, the starting point of the present invention is to provide a novel low-corrosion, low-residue semiconductor cleaning solution, its preparation method and its cleaning application. The cleaning solution is a comprehensive and synergistic use of multiple specific components that can achieve excellent low galvanic corrosion, low metal corrosion performance and low residue, and the cleaning is simple. It has excellent technical effects and application prospects in the field of semiconductor cleaning, thus completing the present invention. Summary of the Invention

[0008] In order to solve the many problems existing in the above-mentioned cleaning solutions and meet the technical requirements of low residue and low corrosion, the inventors of this invention have conducted a lot of in-depth research and exploration, thereby providing a new type of semiconductor cleaning solution, preparation method and cleaning application.

[0009] It should be noted that, in this invention, unless otherwise specified, the specific meaning of "comprising" in relation to composition and description includes both open-ended meanings such as "comprising," "including," etc., and closed-ended meanings such as "composed of," "consisting of," etc., and similar meanings.

[0010] Specifically, the present invention includes the following technical solutions.

[0011] [First technical solution]

[0012] In a first aspect, one technical solution of the present invention is to provide a low-residue, low-corrosion semiconductor cleaning solution (hereinafter sometimes also referred to as "cleaning solution"), said cleaning solution comprising ultrapure water, hexafluorophosphate, organic base, chelating agent and two-component corrosion inhibitor.

[0013] Furthermore, the cleaning solution, by weight, comprises the following components:

[0014]

[0015] In the cleaning solution of the present invention, the mass fraction of ultrapure water is 80-90 parts, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts or 90 parts.

[0016] The ultrapure water is deionized water with a resistance ≥18MΩ.

[0017] In the cleaning solution of the present invention, the hexafluorophosphate is present in parts by weight of 3-8 parts, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts.

[0018] The hexafluorophosphate is selected from any one or a mixture of any of the following: ammonium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, trimethylaniline hexafluorophosphate, 1-n-butyl-3-methylimidazolium hexafluorophosphate, 1-n-propyl-3-methylimidazolium hexafluorophosphate, 1-n-octyl-3-methylimidazolium hexafluorophosphate, 1-n-hexyl-3-methylimidazolium hexafluorophosphate, N-n-butylpyridine hexafluorophosphate, S-(1-oxo-2-pyridine)mercapto-1,3-dimethylpropylurea hexafluorophosphate, and 1-methylpyridinium hexafluorophosphate.

[0019] In the cleaning solution of the present invention, the organic alkali is 10-30 parts by mass, for example, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts.

[0020] The organic base is an aliphatic amine, an aromatic amine, or an alcohol amine.

[0021] The aliphatic amine may be, for example, any one or a mixture of any of the following: 2-ethylhexylamine, diethylamine, n-butylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, N-methyl-N-butylamine and n-dodecylamine;

[0022] The aromatic amine may be, for example, any one or a mixture of any of the following: aniline, N-methylaniline, 2,4-dimethylaniline, N-ethylaniline, diphenylamine, 2-ethylaniline, 4-ethylaniline and p-propylaniline;

[0023] The alkanolamine may be, for example, any one or a mixture of any combination of ethanolamine, N-methylethanolamine, N,N-dimethylethanolamine, N,N-dibutylethanolamine, N-cyclohexylethanolamine, N-phenylethanolamine, N-benzyl-N-methylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-phenyldiethanolamine, N-benzyldiethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, and diethylene glycolamine.

[0024] Preferably, the organic base is any one or a mixture of any combination of ethanolamine, N-methylethanolamine, N,N-dimethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, isopropanolamine, and diethylene glycolamine.

[0025] In the cleaning solution of the present invention, the chelating agent is 0.1-2 parts by mass, for example, 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts.

[0026] The chelating agent is selected from any one or a mixture of any combination of glycine, serine, proline, leucine, alanine, aspartic acid, asparagine, glutamine, valine, lysine, cystine, citric acid, salicylic acid, ethylenediaminetetraacetic acid, malic acid, aminotriacetic acid, hypozoxytriacetic acid, diethylenetriaminepentaacetic acid, tartaric acid, gluconic acid, glycolic acid, hydroxyethylethylenediaminetriacetic acid, hydroxyethylidene diphosphonic acid, hypoaminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid).

[0027] Preferably, the chelating agent is any one or a mixture of any combination of diethylenetriaminepentamethylphosphonic acid and hydroxyethylidene diphosphonic acid.

[0028] In the cleaning solution of the present invention, the mass fraction of the two-component corrosion inhibitor is 0.1-1 parts, for example, it can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part.

[0029] The two-component corrosion inhibitor consists of agent A and agent B, where agent A is at least one of adenosine and guanosine, and agent B is at least one of polyethylene glycol diamine and dimercaptopolyethylene glycol.

[0030] The polyethylene glycol diamine is also commonly abbreviated as NH2-PEG-NH2, and the dimercaptopolyethylene glycol is also commonly abbreviated as SH-PEG-SH.

[0031] In the two-component corrosion inhibitor, the mass ratio of agent A to agent B is 1:0.8-1.5, for example, it can be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5.

[0032] The inventors discovered that the molecular weight of agent B can significantly affect the corrosive and residual properties of the cleaning solution. Preferably, the relative molecular weight of the polyethylene glycol diamine or dimercaptopolyethylene glycol is 400-1500, for example, it can be 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400 or 1500, and most preferably 800-1100.

[0033] The cleaning solution of the present invention can be used in the cleaning process after semiconductor etching. It has excellent low corrosivity and low residue, can be applied in the field of semiconductor technology, and the cleaning is simple, thorough and produces little waste.

[0034] [Second Technical Solution]

[0035] Secondly, one technical solution of the present invention is to provide a method for preparing the above-mentioned cleaning solution.

[0036] The preparation method is as follows: weigh each component according to its respective mass fraction, and then add the hexafluorophosphate, organic base, chelating agent and corrosion inhibitor A and B to ultrapure water at room temperature, and stir and mix thoroughly to obtain a uniform and transparent cleaning solution.

[0037] [Third technical solution]

[0038] Thirdly, one technical solution of the present invention is to provide the use of the cleaning solution in semiconductor chip cleaning.

[0039] The cleaning solution can be used to remove residues after dry etching in the later stages of semiconductor chip manufacturing. It has extremely low galvanic corrosion and metal corrosion on the metal substrate it contacts, and it is easy to rinse clean with very low residue, without affecting subsequent chip device manufacturing processes.

[0040] [Fourth technical solution]

[0041] Fourthly, one technical solution of the present invention provides a cleaning method for silicon oxide materials after dry etching, the cleaning method being as follows:

[0042] At 35-45℃, the silicon oxide substrate after dry etching is immersed in a cleaning solution, or the cleaning solution is sprayed onto the silicon oxide substrate, then rinsed with ultrapure water, and finally dried with nitrogen gas, thus completing the cleaning process of the silicon oxide substrate after dry etching.

[0043] In the cleaning method, the cleaning fluid is the same as that described in the first to third technical solutions above.

[0044] In the cleaning method, the soaking or spraying time is not strictly limited, as long as it can clean thoroughly. For example, it can be 5-20 minutes, such as 5 minutes, 10 minutes, 15 minutes or 20 minutes.

[0045] The ultrapure water is deionized water with a resistance ≥18MΩ.

[0046] The amount of ultrapure water used is not particularly strictly limited, as long as the silicon oxide substrate can be thoroughly rinsed. Those skilled in the art can select the appropriate amount and determine the rinsing endpoint.

[0047] In the cleaning method, the nitrogen gas may be, for example, high-purity nitrogen gas, which may have a volume purity greater than 99.999%.

[0048] Both the ultrapure water and high-purity nitrogen gas mentioned above can be purchased through commercial channels and will not be described in detail here.

[0049] As described above, the present invention provides a cleaning solution for semiconductor cleaning, a preparation method thereof, its uses, and a semiconductor cleaning method using the cleaning solution.

[0050] The cleaning solution of the present invention achieves many excellent technical effects through the optimal selection of multiple components, especially the use of a unique two-component corrosion inhibitor and their synergistic effect. For example, it has excellent low galvanic corrosion, low metal corrosion, excellent low organic residue, and excellent cleaning effect without affecting the subsequent processes of chip components. Attached Figure Description

[0051] Appendix Figure 1 The image shows the Cu-Co potentiodynamic polarization curves using cleaning solution Q1.

[0052] Appendix Figure 2 The image shows the Cu-Co potentiodynamic polarization curves using cleaning solution D1.

[0053] Appendix Figure 3 XPS spectrum of Cu surface on clean silicon oxide substrate.

[0054] Appendix Figure 4 This is the XPS spectrum of the Cu surface on the silicon oxide substrate after Q1 cleaning.

[0055] Appendix Figure 5 This is the XPS spectrum of the Cu surface on the silicon oxide substrate after cleaning with D5. Detailed Implementation

[0056] The present invention will now be described in detail through specific embodiments. However, the uses and purposes of these exemplary embodiments are merely illustrative and are not intended to limit the actual scope of protection of the present invention in any way, nor are they intended to restrict the scope of protection of the present invention to these embodiments.

[0057] In the following examples and performance tests, the ultrapure water used was deionized water with a resistance ≥18MΩ, and will not be described in detail.

[0058] Example 1

[0059] Weigh out 85 parts by weight of ultrapure water, 5.5 parts by weight of 1-n-butyl-3-methylimidazolium hexafluorophosphate, 20 parts by weight of organic base ethanolamine, 1 part by weight of chelating agent hypozinotriacetic acid, and 0.55 parts by weight of a two-component corrosion inhibitor (composed of 0.25 parts by weight of agent A adenosine and 0.3 parts by weight of agent B NH2-PEG-NH2, with a relative molecular weight of 1000 for NH2-PEG-NH2). Then, at room temperature, add the hexafluorophosphate, organic base, chelating agent, and agents A and B of the corrosion inhibitor to the ultrapure water and stir thoroughly to obtain a uniform and transparent cleaning solution, which is named Q1.

[0060] Example 2

[0061] Weigh out 80 parts by weight of ultrapure water, 8 parts of N-n-butylpyridine hexafluorophosphate, 10 parts of organic base N,N-dimethylethanolamine, 2 parts of chelating agent diethylenetriamine pentamethylphosphonic acid, and 0.1 parts of a two-component corrosion inhibitor (composed of 0.04 parts of agent A guanosine and 0.06 parts of agent B NH2-PEG-NH2, with a relative molecular weight of 800) into ultrapure water at room temperature. Then, add the hexafluorophosphate, organic base, chelating agent, and agents A and B of the corrosion inhibitor into the ultrapure water and stir thoroughly to obtain a uniform and transparent cleaning solution, which is named Q2.

[0062] Example 3

[0063] By weight, 90 parts of ultrapure water, 3 parts of hexafluorophosphate S-(1-oxo-2-pyridine)mercapto-1,3-dimethylpropylurea hexafluorophosphate, 30 parts of organic base diethylene glycolamine, 0.1 parts of chelating agent hydroxyethylidene diphosphonic acid, and 1 part of a two-component corrosion inhibitor (composed of 0.44 parts of agent A adenosine and 0.56 parts of agent B SH-PEG-SH, with a relative molecular weight of 1100 for SH-PEG-SH) were weighed out. Then, at room temperature, the hexafluorophosphate, organic base, chelating agent, and agents A and B of the corrosion inhibitor were added to the ultrapure water and stirred thoroughly to obtain a uniform and transparent cleaning solution, which was named Q3.

[0064] Example 4

[0065] Except for replacing adenosine, NH2-PEG-NH2, and 1-n-butyl-3-methylimidazolium hexafluorophosphate in Example 1 with the same amount of guanosine, SH-PEG-SH, and 1-methylpyridinium hexafluorophosphate, everything else remained unchanged, thus obtaining the cleaning solution, which was named Q4.

[0066] Comparative Examples 1-12

[0067] Comparative Examples 1-4: Except for replacing the two-component corrosion inhibitor in Examples 1-4 with the same total amount of single-component agent A, everything else remained unchanged, thus obtaining cleaning solutions, which were named D1, D2, D3 and D4 respectively.

[0068] Comparative Examples 5-8: Except for replacing the two-component corrosion inhibitors in Examples 1-4 with the same total amount of single-component agent B, everything else remained unchanged, thus obtaining cleaning solutions, which were named D5, D6, D7 and D8 respectively.

[0069] Comparative Examples 9-12: Except for replacing the two-component corrosion inhibitors in Examples 1-4 with the same total amount of single-component benzotriazole (BTA), everything else remained unchanged, thus obtaining cleaning solutions, which were named D9, D10, D11 and D12 respectively.

[0070] Comparative Examples 13-16

[0071] Except for replacing the molecular weights of the corresponding B agents in Examples 1-4 with 400, 600, 1300 and 1500 respectively, everything else remained unchanged, thus obtaining the cleaning solutions, which were named D13, D14, D15 and D16 respectively.

[0072] I. Testing of Cu-Co galvanic corrosion in various cleaning solutions

[0073] Using an electrochemical workstation instrument, select potentiodynamic testing, set the scanning potential range to 0.5-1.0V and the scanning speed to 50mV / s in the electrochemical workstation software, obtain the Tafel curve, and then use the software to perform Tafel fitting to obtain the self-corrosion potential value.

[0074] Among them, the appendix Figure 1 The image shows the Cu-Co potentiodynamic polarization curve using cleaning solution Q1. The self-corrosion potential difference |ΔE|=0.032V, indicating that the self-corrosion potential difference is very small, resulting in very little galvanic corrosion.

[0075] The Cu-Co potentiodynamic polarization curves using cleaning solutions Q2-Q4 and the attached... Figure 1 They are highly similar and all have very small self-corrosion potential differences (more specific quantitative data are shown in Table 1 below). Similarly, their galvanic corrosion is very small, and will not be listed here.

[0076] Appendix Figure 2 The image shows the Cu-Co potentiodynamic polarization curve using cleaning solution D1. Its self-corrosion potential difference |ΔE|=0.692V, indicating that its self-corrosion potential difference is relatively large, thus making it prone to galvanic corrosion.

[0077] The Cu-Co potentiodynamic polarization curves using cleaning solution D2-D16 and the attached... Figure 2Height / Generally similar, compared to the attached Figure 1 They have a larger self-corrosion potential difference (more specific quantitative data are shown in Table 1 below), and are also prone to galvanic corrosion, which will not be listed here.

[0078] For a more intuitive comparison, the Cu-Co self-corrosion potential difference |ΔE data of each cleaning solution are listed in Table 1 below.

[0079] Table 1: Cu-Co self-corrosion potential difference of various cleaning solutions |ΔE|

[0080]

[0081] In Table 1 above, " / " indicates the corresponding relationship. For example, taking Q1-Q4 as an example, "0.032 / 0.030 / 0.035 / 0.036" in "|△E|(V)" means that the |△E|(V) of Q1-Q4 are 0.032V, 0.030V, 0.035V and 0.036V respectively. D1-D16 and Table 2 also have the same corresponding relationship, which will not be described in detail here.

[0082] As can be seen from Table 1 above: 1. The cleaning solution of the present invention has excellent low galvanic corrosion performance and can significantly reduce corrosion, which is neither obvious nor unexpected. 2. When the two-component corrosion inhibitor replaces a single agent A or agent B (i.e., D1-D8), it is found that its galvanic corrosion is significantly increased, far worse than Q1-Q4, and D1-D4 is even worse than D5-D8. 3. In contrast, when the two-component corrosion inhibitor is replaced with BTA in the prior art, the reduction in galvanic corrosion is most significant (i.e., D9-D12). 4. The molecular weight of agent B also has a significant impact on galvanic corrosion, with the optimal value being 800-1100. When deviating from this range, a significant increase in galvanic corrosion is found (see D13-D16). This is because the inventors found that the improvement in Cu-Co galvanic corrosion is achieved by increasing the self-corrosion potential of metallic Co, thereby reducing the self-corrosion potential difference between Cu and Co. When the molecular weight of agent B is below 800 or above 1100, it cannot significantly and effectively reduce the potential difference between Cu and Co relative to Q1-Q4: when the molecular weight is below 800, its increase in the self-corrosion potential of Co is limited; while when it is above 1100, it can significantly increase the self-corrosion potential of Co, and it is higher than that of metallic Cu, thus further widening the self-corrosion potential difference between the two. Therefore, the optimal molecular weight of agent B is 800-1100.

[0083] II. Determination of metal corrosion rate of various cleaning solutions

[0084] A 4×4 cm silicon oxide substrate coated with a Cu metal film was immersed in a cleaning solution at 40°C for 15 minutes. After removal, the substrate was thoroughly rinsed with ultrapure water (resistivity ≥18 MΩ) for 3 minutes and finally dried with high-purity nitrogen gas (volume purity >99.999%). The thickness of the metal film before and after cleaning was measured using a four-probe sheet resistance meter. The corrosion rate was calculated as (initial film thickness - post-corrosion film thickness) / cleaning time, with the unit of corrosion rate being... That is, every minute.

[0085] The results of the metal corrosion rates of various cleaning solutions are shown in Table 2 below.

[0086] Table 2: Metal corrosion rates of various cleaning solutions

[0087]

[0088] As can be seen from Table 2 above: 1. The cleaning solution of the present invention exhibits an excellent low metal corrosion rate, which is both unobvious and unexpected. 2. When the two-component corrosion inhibitor replaces a single agent A or agent B (i.e., D1-D8), the metal corrosion rate is found to increase significantly, far worse than Q1-Q4, and D5-D8 is even worse than D9-D12 overall. This proves that the two-component corrosion inhibitor can produce an unexpected synergistic promoting effect. The inventors believe this is because the -NH2 and / or -OH in adenosine / guanosine (agent A) can bind with the -O- in the long chain of NH2-PEG-NH2 / SH-PEG-SH (agent B) through hydrogen bonds, and the molecules of adenosine / guanosine also bind with each other through hydrogen bonds, thus forming a large hydrogen bond network. Furthermore, since the -NH2, -OH, and -SH groups possess lone pairs of electrons, they can coordinate with metals containing empty orbitals. Thus, the large hydrogen bond network and coordination interactions mutually promote each other, resulting in a dense adsorption film on the metal surface. This ensures excellent protection of the metal during cleaning, leading to an extremely low metal corrosion rate. 3. The molecular weight of agent B has a significant impact on the metal corrosion rate. When the molecular weight is higher than 1100 or lower than 800, the metal corrosion rate increases (see D13-D16), but is still significantly better than D1-D12. The inventors believe the main reason is likely that when the -PEG- chain in agent B is too long, chain folding is more likely to occur, resulting in more intramolecular hydrogen bonds in agent B, leading to a reduction in the number of hydrogen bonds formed with agent A, making it impossible to form a high-density adsorption film on the metal surface. Conversely, when the -PEG- chain is too short, the overall hydrogen bond density is low, also failing to form a dense adsorption film layer on the metal surface. Therefore, the optimal molecular weight of agent B is 800-1100; only within this range can the best technical effect be achieved.

[0089] III. Test for organic residue on metal surface after cleaning

[0090] The silicon oxide substrates coated with Cu metal films after the above "II" cleaning were subjected to photoelectron spectroscopy (XPS) using a Thermo Kalpha instrument. The peak at the binding energy of ~400 eV is the N1s peak of nitrogen-containing compounds, so the residual state of the passivation film on the metal surface can be determined by the peak area.

[0091] in:

[0092] Appendix Figure 3 The XPS spectrum of the Cu surface on a clean silicon oxide substrate (i.e., without the cleaning process described above, "II") has an N1s integral of 2560.3.

[0093] Appendix Figure 4 The image shows the XPS spectrum of the Cu surface on the silicon oxide substrate after Q1 cleaning. Its N1s integral is 4344.4, indicating that the organic residue on the metal surface is very small, achieving an excellent low-residue effect.

[0094] Appendix Figure 5 The image shows the XPS spectrum of the Cu surface of the silicon oxide substrate after cleaning with D5. Its N1s integral is 60350.5, indicating that there is a lot of organic residue on the metal surface, which is far inferior to the cleaning effect of Q1.

[0095] For the sake of length and brevity, the XPS spectra of other cleaning solutions are not listed one by one, but are still listed in Table 3 below.

[0096] Table 3: N1s integral of XPS spectra of metal surfaces after cleaning

[0097]

[0098] As can be seen from Table 3 above: 1. The cleaning solution of the present invention has excellent low-residue effect, which is both obvious and unexpected. 2. When the two-component corrosion inhibitor replaces single agent A or agent B (i.e., D1-D8), it is found that the surface residue is significantly increased, far worse than Q1-Q4, and D5-D8 is also significantly worse than D1-D4, and even significantly worse than D9-D12 using BTA. This proves that agent B has a greater impact than agent A on organic residue. This proves that the two-component corrosion inhibitor of the present invention can produce excellent low-residue surface effect. This is because during the rinsing stage, ultrapure water continuously rinses or wets the wafer surface, causing the intermolecular hydrogen bond network of the organic adsorption film (passivation film) on the wafer metal surface to be easily destroyed, while agents A and B can re-form new hydrogen bonds with water, thus being completely removed by simple rinsing or wetting. 3. When the molecular weight of agent B was changed, the surface residue was found to increase (see D13-D16), but it was still significantly better than D1-D12. Therefore, the optimal molecular weight of agent B is 800-1100.

[0099] As described above, the present invention provides a low-corrosion, low-residue semiconductor cleaning solution, its preparation method, its uses, and a cleaning method using the same. The cleaning solution achieves numerous excellent technical effects through the use of a specific two-component corrosion inhibitor, particularly excellent low galvanic corrosion, low metal corrosion, and excellent low organic residue. Furthermore, it provides excellent cleaning performance without affecting subsequent processes of the chip components, thus demonstrating promising application prospects and practical value in the field of semiconductor cleaning.

[0100] It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the invention. Furthermore, it should be understood that after reading the technical description of this invention, those skilled in the art can make various alterations, modifications, and / or variations to the invention, and all such equivalent forms also fall within the scope of protection defined by the appended claims.

Claims

1. A low-residue, low-corrosion semiconductor cleaning solution, wherein the cleaning solution comprises, by weight, the following components: Ultrapure water 80-90 Hexafluorophosphate 3-8 Organic base 10-30 Chelating agent 0.1-2 Two-component corrosion inhibitor 0.1-1 The two-component corrosion inhibitor consists of agent A and agent B, where agent A is at least one of adenosine and guanosine, and agent B is at least one of polyethylene glycol diamine and dimercaptopolyethylene glycol; in, The relative molecular weight of the polyethylene glycol diamine or dimercaptopolyethylene glycol is 800-1100; The hexafluorophosphate is selected from any one or a mixture of any combination of ammonium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, trimethylaniline hexafluorophosphate, 1-n-butyl-3-methylimidazolium hexafluorophosphate, 1-n-propyl-3-methylimidazolium hexafluorophosphate, 1-n-octyl-3-methylimidazolium hexafluorophosphate, 1-n-hexyl-3-methylimidazolium hexafluorophosphate, N-n-butylpyridine hexafluorophosphate, S-(1-oxo-2-pyridine)mercapto-1,3-dimethylpropylurea hexafluorophosphate, and 1-methylpyridinium hexafluorophosphate.

2. The semiconductor cleaning solution as described in claim 1, characterized in that: The chelating agent is selected from any one or a mixture of any combination of glycine, serine, proline, leucine, alanine, aspartic acid, asparagine, glutamine, valine, lysine, cystine, citric acid, salicylic acid, ethylenediaminetetraacetic acid, malic acid, hypozoxytriacetic acid, diethylenetriaminepentaacetic acid, tartaric acid, gluconic acid, glycolic acid, hydroxyethylethylenediaminetriacetic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid).

3. The semiconductor cleaning solution as described in claim 2, characterized in that: The chelating agent is any one or a mixture of any combination of nitrotriacetic acid, diethylenetriaminepentamethylphosphonic acid, and hydroxyethylidene diphosphonic acid.

4. A method for preparing the semiconductor cleaning solution according to any one of claims 1-3, wherein the preparation method specifically comprises: weighing each component in its respective mass fraction, and then adding the hexafluorophosphate, organic base, chelating agent and corrosion inhibitor A and B to ultrapure water at room temperature, and stirring and mixing thoroughly to obtain the cleaning solution.

5. The use of the semiconductor cleaning solution according to any one of claims 1-3 in semiconductor chip cleaning.

6. A cleaning method for a silicon oxide substrate after dry etching, wherein the cleaning method is as follows: At 35-45℃, the silicon oxide substrate after dry etching is immersed in a cleaning solution, or the cleaning solution is sprayed onto the silicon oxide substrate, then rinsed with ultrapure water, and finally dried with nitrogen gas, thus completing the cleaning process of the silicon oxide substrate after dry etching. The cleaning solution is the semiconductor cleaning solution according to any one of claims 1-3.

7. The cleaning method as described in claim 6, characterized in that: The soaking or spraying time is 5-20 minutes.

8. The cleaning method as described in claim 6 or 7, characterized in that: The nitrogen gas is nitrogen gas with a volume purity greater than 99.999%.

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