Cleaning composition, cleaning device and method for manufacturing semiconductor device using the same

Abstract

Disclosed are a cleaning composition, a cleaning apparatus, and a method for manufacturing a semiconductor device. The cleaning composition comprises: a surfactant; deionized water; and an organic solvent, wherein the surfactant is included in the cleaning composition at a concentration of about 0.28 M to about 0.39 M or a molar fraction of about 0.01 to about 0.017, and wherein the organic solvent is included in the cleaning composition at a concentration of about 7.1 M to about 7.5 M or a molar fraction of about 0.27 to about 0.35.

Description

[0001] The entire contents of Korean Patent Application No. 10-2018-0015263, entitled “Cleaning Composition, Cleaning Apparatus, and Method of Fabricating Semiconductor Device Using the Same,” filed on February 7, 2018 in the Korean Intellectual Property Office are incorporated herein by reference. Technical Field

[0002] Embodiments relate to a cleaning composition, a cleaning apparatus, and a method of manufacturing a semiconductor device using the cleaning composition and the cleaning apparatus. Background Art

[0003] As semiconductor devices become highly integrated, fine patterns and multi-layered circuit structures can be formed. Summary of the invention

[0004] An embodiment can be achieved by providing a cleaning composition comprising: a surfactant; deionized water; and an organic solvent, wherein the surfactant is included in the cleaning composition at a concentration of about 0.28M to about 0.39M or a mole fraction of about 0.01 to about 0.017, and wherein the organic solvent is included in the cleaning composition at a concentration of about 7.1M to about 7.5M or a mole fraction of about 0.27 to about 0.35.

[0005] An embodiment can be implemented by providing a cleaning device for cleaning a substrate, the cleaning device comprising: a chuck on which the substrate is receivable; a nozzle configured to supply a cleaning liquid to the substrate; and a cleaning liquid supply portion configured to supply the cleaning liquid to the nozzle and configured to generate cleaning particles by stirring the cleaning liquid, wherein the cleaning liquid supply portion comprises a conductivity meter configured to measure the conductivity of the cleaning liquid and a thermostat configured to cool the cleaning liquid when the conductivity of the cleaning liquid decreases.

[0006] An embodiment may be implemented by providing a method for manufacturing a semiconductor device, the method comprising: preparing a cleaning solution; cleaning a substrate using the cleaning solution; and drying the substrate, wherein the step of preparing the cleaning solution comprises providing deionized water into a chemical tank and generating the cleaning solution by mixing a chemical source of the cleaning solution in the deionized water, wherein the cleaning solution comprises a surfactant, deionized water, and an organic solvent, wherein the surfactant is included in the cleaning solution at a concentration of about 0.004M to about 0.04M or a molar fraction of about 0.0003 to about 0.0004, and wherein the organic solvent is included in the cleaning solution at a concentration of about 0.17M to about 0.57M or a molar fraction of about 0.005 to about 0.008. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Features will become apparent to those skilled in the art by describing in detail exemplary embodiments with reference to the accompanying drawings, in which:

[0008] Figure 1 A plan view showing an apparatus for manufacturing a semiconductor device according to an exemplary embodiment of the present disclosure;

[0009] Figure 2 Shows Figure 1 A schematic diagram of an example of a cleaning device shown in ;

[0010] Figure 3 shows a graph presenting the cleaning efficiency of chemical solutions and Standard Clean 1 (SC-1) solution as a function of the size of process particles;

[0011] Figure 4 Shows Figure 2 A schematic diagram of an example of a chemical solution supply unit shown in FIG.

[0012] Figure 5A and Figure 5B Shows Figure 4 A perspective view of an example of a cleaning particle;

[0013] Figure 6 shows a graph presenting a process particle removal efficiency of a chemical solution with cleaning particles and a process particle removal efficiency of a chemical solution without cleaning particles;

[0014] Figure 7 shows a graph presenting a change in primary particle removal efficiency of cleaning particles to process particles as a function of the height of the cleaning particles;

[0015] Figure 8 The secondary particle removal efficiency of cleaning particles to process particles is shown according to Figure 4 A diagram showing the change in pressure of the chemical solution in the circulation pipeline and the pump;

[0016] Fig. 9 Shows the use of Figure 1 A flowchart of a method for manufacturing a semiconductor device using an apparatus;

[0017] Fig.10 Shows the preparation Fig. 9 A flow chart of the steps of preparing a chemical solution;

[0018] Fig.11 Shows Figure 4 A perspective view of a seed of a clean particle;

[0019] Fig.12 showing a graph presenting the conductivity of the chemical solution at a second temperature and the conductivity of the chemical solution at ambient temperature;

[0020] Fig.13 showing a graph representing a change in conductivity of a chemical solution according to a concentration of an organic solvent in the chemical solution; and

[0021] Fig.14 The height of the cleaning particles is shown according to Figure 4 Graph of the change in pressure of the chemical solution in the circulation line and pump. DETAILED DESCRIPTION

[0022] Figure 1 A plan view of an apparatus for manufacturing a semiconductor device according to an exemplary embodiment of the present disclosure is shown.

[0023] Reference Figure 1 The apparatus 100 for manufacturing a semiconductor device may include a wet cleaning apparatus or a wet etching apparatus. In an embodiment, the apparatus 100 may include a chemical mechanical polishing (CMP) apparatus. The apparatus 100 may include an index apparatus 110, a conveying apparatus 120, a cleaning apparatus 130, and a drying apparatus 140.

[0024] The indexing device 110 may temporarily store a cassette 118. The cassette 118 may have a substrate W mounted thereon (e.g., the substrate W may be mountable on the cassette 118). The indexing device 110 may include a loading port 112 and a transport frame 114. The loading port 112 may accommodate the cassette 118. The cassette 118 may include a front opening wafer transport box (FOUP). The indexing arm 116 in the transport frame 114 may load the substrate W from the cassette 118 and may transfer the substrate W to the transfer device 120. In addition, the indexing arm 116 may unload the substrate W in the cassette 118.

[0025] The conveying device 120 may convey the substrate W to the cleaning device 130 and to the drying device 140. The conveying device 120 may include a buffer chamber 122 and a conveying chamber 124. The buffer chamber 122 may be disposed between the transport frame 114 and the conveying chamber 124. The buffer arm 123 in the buffer chamber 122 may accommodate the substrate W. The indexing arm 116 may provide the substrate W to the buffer arm 123. The indexing arm 116 may transfer the substrate W on the buffer arm 123 to the box 118. The conveying arm 125 in the conveying chamber 124 may provide the substrate W on the buffer arm 123 to the cleaning device 130. In addition, the conveying arm 125 may transfer the substrate W from the cleaning device 130 to the drying device 140. In addition, the conveying arm 125 may transfer the substrate W from the cleaning device 130 to the buffer arm 123.

[0026] The cleaning device 130 may be disposed on one side of the transfer chamber 124. The cleaning device 130 may clean and / or etch the substrate W. In an embodiment, the cleaning device 130 may wet clean the substrate W. In an embodiment, the cleaning device 130 may dry clean the substrate W.

[0027] The drying device 140 may be disposed on the other side of the transfer chamber 124. The drying device 140 may dry the substrate W. For example, the drying device 140 may include a supercritical treatment device. In an embodiment, the drying device 140 may include a calciner and / or a heater.

[0028] In an embodiment, a polishing device may be disposed at an end of the transfer chamber 124 to face the buffer chamber 122. The polishing device may polish the substrate W. For example, the polishing device may be a CMP device.

[0029] Figure 2 Shows Figure 1 An example of a cleaning device 130 is shown.

[0030] Reference Figure 2 The cleaning device 130 may include, for example, a chuck 310 , a pawl 320 , first and second arms 332 and 334 , first and second nozzles 342 and 344 , a first deionized water supplier 350 , and a chemical solution supplier 360 .

[0031] The chuck 310 may accommodate the substrate W. The chuck 310 may rotate the substrate W. For example, the chuck 310 may rotate the substrate W at a rotation speed of about 10 rpm to about 6000 rpm. Therefore, the first deionized water 132 or the chemical solution 134 may move on the substrate W by centrifugal force, and thus, the substrate W may be cleaned.

[0032] The pawl 320 may surround the substrate W. The first deionized water 132 or the chemical solution 134 may move in a direction from the substrate W to the pawl 320. The pawl 320 may help prevent the first deionized water 132 or the chemical solution 134 on the rotating substrate W from flowing out. The pawl 320 may release the first deionized water 132 or the chemical solution 134 under the chuck 310. The pawl 320 may help prevent contamination of the substrate W.

[0033] The first arm 332 and the second arm 334 may respectively fix the first nozzle 342 and the second nozzle 344. The first nozzle 342 may be connected to the top end of the first arm 332. The second nozzle 344 may be connected to the top end of the second arm 334. The first arm 332 and the second arm 334 may respectively move the first nozzle 342 and the second nozzle 344 to the center of the substrate W.

[0034] The first nozzle 342 and the second nozzle 344 may provide the first deionized water 132 and the chemical solution 134 onto the substrate W, respectively. For example, the first nozzle 342 and the second nozzle 344 may provide the first deionized water 132 and the chemical solution 134, respectively, at a pressure of about 1 atm to about 10 atm. The first deionized water 132 and the chemical solution 134 may be provided in the form of droplets or sprays. The first deionized water 132 and the chemical solution 134 may be provided to the center of the substrate W. The first deionized water 132 and the chemical solution 134 may clean the substrate W from the center to the edge. The first deionized water 132 and the chemical solution 134 may help remove process particles 136 from the substrate W.

[0035] The first deionized water supplier 350 may provide the first deionized water 132 to the first nozzle 342. The first deionized water 132 may be a cleaning solution and / or an etchant. For example, the first deionized water supplier 350 may include a water purifier.

[0036] The chemical solution supply part 360 may supply the chemical solution 134 to the second nozzle 344. The chemical solution 134 may be an etchant and / or a cleaning composition. For example, the chemical solution 134 may have a pH of about 8 or more. If the pH of the chemical solution 134 is higher than 9, the repulsive force between the process particles 136 in the chemical solution 134 may increase. In addition, if the pH of the chemical solution 134 is higher than 9, the repulsive force between the substrate W and the process particles 136 in the chemical solution 134 may increase.

[0037] For example, the chemical solution 134 may include a surfactant, a second deionized water 514 (see Figure 4) and an organic solvent. The organic solvent may include, for example, isopropyl alcohol (IPA), ethanol (EtOH), methanol (MeOH), dimethyl sulfoxide (DMOS), dimethylformamide (DMF), ethylene glycol (EG), propylene glycol (PG), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP). In an embodiment, the organic solvent may include, for example, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, ethylene glycol, propylene glycol or N-methyl-2-pyrrolidone. The surfactant may be an anionic surfactant. In an embodiment, the surfactant may be a sulfate compound represented by Formula 1.

[0038] (R 1 -O) a -(R 2 -O) b -SO 3 NH 4 (1)

[0039] In Formula 1, a and b may each independently be an integer of, for example, 0 to 18. In an embodiment, a and b may not be zero at the same time. 1 and R 2 and R are each independently, for example, a substituted or unsubstituted alkyl or alkylene group having 1 to 18 carbon atoms or a substituted or unsubstituted aryl or arylene group having 6 to 14 carbon atoms. In an embodiment, when a is 3 or greater (e.g., 3 to 18), (R 1 -O) may be repeated randomly or in block form. When b is 3 or greater (e.g., 3 to 18), (R 2 -O) may be repeated randomly or in block form. In an embodiment, when a=1, R 1 It may have 16 carbon atoms and when b=0, the surfactant may be hexadecyl ammonium sulfate (CH 3 (CH 2 ) 14 CH 2 -O-SO 3 NH 4 ). In the embodiment, when a=1, R 1 It can have 12 carbon atoms, b=3, R 2 It may have 2 carbon atoms, and the surfactant may be ammonium lauryl ether sulfate (CH 3 (CH 2 ) 10 CH 2 -O-(CH 2 CH 2 -O) 3 -SO 3NH 4 ). The surfactant may help improve the efficiency of removing process particles 136.

[0040] Figure 3 A graph presenting the cleaning efficiency of a chemical solution 134 according to an embodiment and a standard clean 1 (SC-1) solution on process particles 136 of various sizes is shown.

[0041] Reference Figure 3 , when the process particles 136 have a size of about 100 nm or less, the cleaning efficiency (362) of the chemical solution 134 may be higher than the cleaning efficiency (364) of the SC-1 solution. For example, for process particles 136 having a size of about 45 nm or less, the chemical solution 134 may have a cleaning efficiency (362) of about 87%, and the SC-1 solution may have a cleaning efficiency (364) of only about 21%. The SC-1 solution may be provided at a high pressure of about 2 atm. Due to the high pressure of the SC-1 solution, the top surface of the substrate W may be damaged, thereby undesirably generating new process particles 136. For example, fine and / or small process particles 136 having a size of about 45 nm or less may not be easily removed. On the other hand, the chemical solution 134 according to an embodiment may be provided at a relatively low pressure (e.g., a pressure of about 1 atm) or at atmospheric pressure, and the surfactant of the chemical solution 134 may adsorb and remove the fine process particles 136. Therefore, the cleaning efficiency (362) of the chemical solution 134 may be higher than the cleaning efficiency (364) of the SC-1 solution.

[0042] Figure 4 Shows Figure 2 An example of a chemical solution supply portion 360 .

[0043] Reference Figure 4 , the chemical solution supply part 360 may circulate the chemical solution 134. In addition, the chemical solution supply part 360 may stir and / or mix the chemical solution 134. The chemical solution supply part 360 may include a source supply part 410, a deionized water supply part 420, and a cleaning solution circulator 430.

[0044] The source supply 410 may store a chemical source 512. The chemical source 512 may include deionized water, a surfactant, and an organic solvent. In an embodiment, the chemical source 512 may include about 30wt% of a surfactant / organic solvent and about 70wt% of deionized water. For example, the surfactant may have a concentration of about 0.28M to about 0.39M in the chemical source 512 (e.g., or a molar fraction of about 0.01 to about 0.017), and the organic solvent may have a concentration of about 7.1M to about 7.5M in the chemical source 512 (e.g., or a molar fraction of about 0.27 to about 0.35). In an embodiment, the chemical source 512 may include about 70wt% of a surfactant / organic solvent and about 30wt% of deionized water. The chemical source 512 may be maintained at ambient temperature (e.g., maintained at a temperature of about 20°C). The source supply 410 may be connected to the cleaning liquid circulator 430 via the first supply line 412 and the first source valve 414 and the second source valve 416.

[0045] The deionized water supply 420 may store the second deionized water 514. The second deionized water 514 may be maintained at ambient temperature (eg, may be maintained at a temperature of about 20°C). The deionized water supply 420 may be connected to the cleaning liquid circulator 430 via a second supply line 422 and first and second water valves 424 and 426.

[0046] The cleaning liquid circulator 430 can generate the chemical solution 134 by mixing the chemical source 512 and the second deionized water 514. For example, the chemical source 512 can be diluted by about 10 times to about 100 times with the second deionized water 514. The organic solvent can have a concentration of about 0.17M to about 0.57M in the chemical solution 134 (e.g., or a mole fraction of about 0.005 to about 0.008). The surfactant can have a concentration of about 0.004M to about 0.04M in the chemical solution 134 (e.g., or a mole fraction of about 0.0003 to about 0.0004). For example, the chemical source 512 can be diluted by about 10 to about 20 times with the second deionized water 514. In an embodiment, the organic solvent can have a concentration of about 0.4M in the chemical solution 134. The surfactant can have a concentration of about 0.022M in the chemical solution 134.

[0047] The cleaning liquid circulator 430 can generate cleaning particles 418 in the chemical solution 134 by circulating the chemical solution 134. For example, the cleaning liquid circulator 430 can generate the cleaning particles 418 in about one hour. The cleaning liquid circulator 430 may include a first chemical tank 440, a circulation line 450, a pump 460, an agitator 470, a second chemical tank 480, a discharge line 490, a conductivity meter 500, a thermostat 600, and a controller 700.

[0048] The first chemical tank 440 may stir the second deionized water 514 and the chemical source 512. The first chemical tank 440 may store the chemical solution 134.

[0049] The circulation line 450 may be branched from the bottom of the first chemical tank 440 and may be connected to the top of the first chemical tank 440. Similarly, the circulation line 450 may be branched from the bottom of the second chemical tank 480 and may be connected to the top of the second chemical tank 480. The first chemical tank 440 may be connected to the second chemical tank 480 via the circulation line 450. The chemical solution 134 may be circulated from the lower part of the first chemical tank 440 and the second chemical tank 480 along the circulation line 450 to the upper part of the first chemical tank 440 and the second chemical tank 480. For example, the circulation line 450 may have a length of about 15 m or more from the bottom to the top of the first chemical tank 440. The circulation valve 452 may be coupled to the circulation line 450 between the top of the first chemical tank 440 and the second chemical tank 480 and the pump 460. The circulation valve 452 may control the circulation of the chemical solution 134 in the circulation line 450. For example, the circulation valve 452 may be a three-way valve. The circulation valve 452 may provide the chemical solution 134 in the circulation line 450 to at least one of the first chemical tank 440 and the second chemical tank 480 according to a control signal from the controller 700 .

[0050] The pump 460 may be disposed between the first chemical tank 440 and the second chemical tank 480. The pump 460 may be connected to the circulation line 450. The pump 460 may generate a circulation pressure and / or a pumping pressure for the chemical solution 134. The chemical solution 134 may circulate at a flow rate proportional to the circulation pressure and / or the pumping pressure generated by the pump 460. For example, the pump 460 may circulate the chemical solution 134 at a pumping pressure of about 200 KPa or greater. The circulation valve 452 may divide and / or distribute the pumping pressure for the chemical solution 134.

[0051] The agitator 470 may be connected to the end of the circulation line 450 in the first chemical tank 440. The agitator 470 may be disposed adjacent to the bottom of the first chemical tank 440. The agitator 470 may extend parallel to the bottom of the first chemical tank 440. For example, the agitator 470 may include a porous tube. For example, the agitator 470 may include a perforation 472. The perforation 472 may be disposed to face the opposite side of the bottom of the first chemical tank 440 (e.g., facing the top of the first chemical tank 440). The perforation 472 may generate a vortex flow of the chemical solution 134, and thus the chemical solution 134 may be effectively agitated.

[0052] The agitator 470 can generate cleaning particles 418 and / or adsorbed particles in the chemical solution 134. The cleaning particles 418 may be different from typical micelles. Generally, micelles may be generated when a critical micelle concentration is reached. On the other hand, the cleaning particles 418 may be generated by reducing the solubility of the chemical solution 134. For example, when the saturation concentration of the chemical solution 134 is reached, the cleaning particles 418 of the chemical solution 134 may be generated. When the chemical solution 134 is stirred, the distribution of the cleaning particles 418 may be changed.

[0053] The second chemical tank 480 may store the spare chemical solution 134. The chemical solution 134 in the second chemical tank 480 may be circulated through the circulation line 450 and the pump 460. The second chemical tank 480 may include a baffle 482. The baffle 482 may be disposed in the second chemical tank 480 adjacent to the circulation line 450 and the discharge line 490. The baffle 482 may generate a vortex flow of the chemical solution 134 in the second chemical tank 480, and thus the chemical solution 134 may be effectively stirred.

[0054] The discharge line 490 may connect the first chemical tank 440 and the second chemical tank 480 to the second nozzle 344. The discharge valve 492 may be coupled to the discharge line 490 between the first chemical tank 440 and the second chemical tank 480 and the second nozzle 344. The discharge valve 492 may control the supply of the chemical solution 134.

[0055] The conductivity meter 500 may be provided in the first chemical tank 440 or combined with the first chemical tank 440. The conductivity meter 500 may measure the conductivity of the chemical solution 134.

[0056] The thermostat 600 may be coupled to the circulation line 450. The thermostat 600 may be coupled to the first chemical tank 440 and the second chemical tank 480. The thermostat 600 may control the temperature of the chemical solution 134. For example, the thermostat 600 may heat and / or cool the chemical solution 134.

[0057] The controller 700 may be connected to the conductivity meter 500 and the thermostat 600. The controller 700 may use conductivity to control the generation and / or growth of the cleaning particles 418. In addition, the controller 700 may control the opening and closing of the pump 460, the first and second water valves 424 and 426, the first and second source valves 414 and 416, and the circulation valve 452.

[0058] Figure 5A and Figure 5B Shows Figure 4 A perspective view of an example of cleaning particles 418 .

[0059] Reference Figure 5A and Figure 5B, each of the cleaning particles 418 may be formed by self-assembly of surfactant molecules 156. The surfactant molecules 156 may be arranged in one direction in each cleaning particle 418. Each of the surfactant molecules 156 may include a hydrophobic unit 155 and a hydrophilic unit 157. The hydrophobic unit 155 may include (R 1 -O) a -(R 2 -O) b -, where R 1 , R 2 , a and b are the same as described above. The hydrophilic unit 157 may include a sulfite group (-SO 3 - ) or a salt thereof. The hydrophobic unit 155 may be combined with the hydrophilic unit 157 in one direction.

[0060] Reference Figure 5A , the cleaning particles 418 may be hexahedral, whereas typical micelles are spherical. For example, the cleaning particles 418 may have a horizontal length L of about 20 μm to about 200 μm. 1 and vertical length L 2 and a height T (eg, thickness) of about 1 μm to about 10 μm. The height T of the cleaning particles 418 may be defined along a direction along which the surfactant molecules 156 are arranged or extended.

[0061] Reference Figure 5B , the cleaning particles 418 may have a hexahedral or cubic shape. For example, the horizontal length L of the cleaning particles 418 is 1 , vertical length L 2 The horizontal length L of the cleaning particle 418 may be about 20 μm to about 200 μm. 1 , vertical length L 2 The average horizontal length, average vertical length, and average height T of the cleaning particles 418 will be described below, respectively.

[0062] Figure 6 A graph presenting the particle removal efficiency ( 413 ) of the chemical solution 134 with cleaning particles 418 and the particle removal efficiency ( 415 ) of the chemical solution 134 without cleaning particles 418 is shown.

[0063] Reference Figure 6, because the cleaning particles 418 can adsorb and remove the process particles 136, the particle removal efficiency (413) of the chemical solution 134 having the cleaning particles 418 can be higher than the particle removal efficiency (415) of the chemical solution 134 without the cleaning particles 418. For example, the chemical solution 134 having the cleaning particles 418 can have a particle removal efficiency of about 81.0%, while the chemical solution 134 without the cleaning particles 418 can have a particle removal efficiency of about 9.8%.

[0064] Figure 7 A graph presenting changes in the primary particle removal efficiency ( 411 ) of the cleaning particles 418 to the process particles 136 according to the height T of the cleaning particles 418 is shown.

[0065] Reference Figure 7 As the size of the cleaning particles 418 increases, the primary particle removal efficiency (411) of the cleaning particles 418 to the process particles 136 may increase. For example, a cleaning particle 418 having a height T of about 10 μm may have a primary particle removal efficiency (411) of about 20%, a cleaning particle 418 having a height T of about 50 μm may have a particle removal efficiency (411) of about 80%, and a cleaning particle 418 having a height T of about 100 μm may have a primary particle removal efficiency (411) of about 90%. If the height T of the cleaning particle 418 is greater than the horizontal length L of the cleaning particle 418 1 and vertical length L 2 , the cleaning particles 418 may damage the substrate W. For example, if the cleaning particles 418 have a height T of about 200 μm or more, the substrate W may be damaged by the cleaning particles 418. Therefore, the yield of the substrate W may be reduced.

[0066] As the speed at which the chemical solution 134 is stirred increases, the primary particle removal efficiency (411) of the cleaning particles 418 to the process particles 136 may increase. The speed at which the chemical solution 134 is stirred may be defined as the flow rate per minute of the chemical solution 134 through the circulation line 450. For example, when the chemical solution 134 is stirred at a speed of 20 liters per minute (lpm), the primary particle removal efficiency (411) of the cleaning particles 418 to the process particles 136 may be about 60% to about 80%. The cleaning particles 418 may be formed as hexahedrons having a height T of about 1 μm to about 10 μm. When the chemical solution 134 is stirred at a speed less than 20 lpm, the primary particle removal efficiency (411) of the cleaning particles 418 to the process particles 136 may be about 60% or less. When the chemical solution 134 is not stirred, it may be difficult to produce the cleaning particles 418.

[0067] Figure 8The secondary particle removal efficiency ( 417 ) of the chemical solution 134 in the circulation line 450 and the pump 460 for the process particles 136 is shown as a function of the pressure of the chemical solution 134 .

[0068] Reference Figure 8 , the secondary particle removal efficiency (417) of the chemical solution 134 to the process particles 136 may be proportional to the pressure of the chemical solution 134 (e.g., the pressure of the pumped chemical solution). As the pressure of the chemical solution 134 increases, the speed of stirring the chemical solution 134 increases, and thus, the height T of the cleaning particles 418 may increase to about 1 μm to about 10 μm. Therefore, as the pressure of the chemical solution 134 increases, the secondary particle removal efficiency (417) of the chemical solution 134 to the process particles 136 may increase. For example, when the pressure of the chemical solution 134 is 0 KPa, the secondary particle removal efficiency (417) of the chemical solution 134 to the process particles 136 may be about 20% or less. When the pressure of the chemical solution 134 is 100 KPa, the secondary particle removal efficiency (417) of the chemical solution 134 to the process particles 136 may increase to about 60% or more.

[0069] Hereinafter, a method of manufacturing a semiconductor device using the apparatus 100 will be described.

[0070] Fig. 9 A flow chart of a method of manufacturing a semiconductor device using the apparatus 100 is shown.

[0071] Reference Fig. 9 The method for manufacturing a semiconductor device may include a cleaning method. The method for manufacturing a semiconductor device may include a step of preparing a chemical solution 134 (S100), a step of cleaning a substrate W (S200), and a step of drying the substrate W (S300).

[0072] The chemical solution supplier 360 of the cleaning device 130 may prepare the chemical solution 134 (S100). The step of preparing the chemical solution 134 (S100) may include a step of preparing a cleaning liquid.

[0073] Fig.10 Shows the preparation Fig. 9 A flow chart of the steps of preparing a chemical solution 134.

[0074] Reference Fig.10, the step of preparing the chemical solution 134 (S100) may include the following steps: providing deionized water (S110), mixing the chemical source 512 (S120), heating the chemical solution 134 (S130), detecting the conductivity of the chemical solution 134 (S140), determining whether the conductivity of the chemical solution 134 decreases (S150), cooling the chemical solution 134 (S160), and determining whether the conductivity of the chemical solution 134 is saturated (S170).

[0075] The deionized water supplier 420 may provide the second deionized water 514 into the first chemical tank 440 (S110). The first water valve 424 or the first water valve 424 and the second water valve 426 may be opened.

[0076] The source supply part 410 may provide the chemical source 512 into the first chemical tank 440, and may mix the chemical source 512 with the second deionized water 514 (S120). When the first water valve 424 and the second water valve 426 are closed, the first source valve 414 or the first source valve 414 and the second source valve 416 may be opened. The chemical source 512 may be diluted by about 10 times to about 100 times with the second deionized water 514. For example, the chemical source 512 may be diluted by about 10 times to about 20 times with the second deionized water 514.

[0077] Fig.11 Shows Figure 4 A perspective view of a seed 419 of a cleaning particle 418 .

[0078] Reference Figure 4 , Fig.10 and Fig.11 , the thermostat 600 can generate seeds 419 of cleaning particles 418 in the chemical solution 134 by heating the chemical solution 134 (S130). By heating the chemical solution 134 to a first temperature (e.g., a temperature of about 26°C) higher than the ambient temperature (e.g., a temperature of about 20°C) for about ten minutes, seeds 419 can be generated in the chemical solution 134, and the seeds 419 can be plate-shaped. The horizontal length and vertical length of the seeds 419 can be respectively greater than the height of the seeds 419. The horizontal length and vertical length of the seeds 419 can be respectively about 20 μm to about 200 μm, and the height of the seeds 419 can be about 1 μm or less. The height of the seeds 419 may not be limited. In an embodiment, the horizontal length and vertical length and the height of the seeds 419 can all be about 1 μm or less.

[0079] Reference Figure 4 and Fig.10, the conductivity meter 500 may detect the conductivity of the chemical solution 134 (S140). For example, the conductivity meter 500 may detect the conductivity of the chemical solution 134 for about one minute to ten minutes. The conductivity of the chemical solution 134 may be determined based on the binding state between the surfactant molecules 156 in the chemical solution 134 or between the hydrophobic unit 155 and the hydrophilic unit 157.

[0080] The controller 700 may determine whether the conductivity of the chemical solution 134 decreases (e.g., has decreased) (S150). For example, as the surfactant molecules 156 agglomerate, the conductivity of the chemical solution 134 may decrease. When the hydrophobic unit 155 and the hydrophilic unit 157 have not yet been combined, the conductivity of the chemical solution 134 may be about 500 μs / cm or higher. Once the hydrophobic unit 155 and the hydrophilic unit 157 are combined or have been combined, the conductivity of the chemical solution 134 may be about 500 μs / cm or lower (e.g., lower than an initial value of about 500 μs / cm or higher). Therefore, when the seeds 419 are generated in the chemical solution 134, the conductivity of the chemical solution 134 may decrease. For example, if the conductivity of the chemical solution 134 decreases by about 2%, the controller 700 may determine that the seeds 419 have been generated in the chemical solution 134.

[0081] If it is determined that seeds 419 have been generated in the chemical solution 134, the thermostat 600 may grow cleaning particles 418 from the seeds 419 by cooling the chemical solution 134 (e.g., may promote or otherwise provide momentum for the growth of the cleaning particles 418). The height T of the cleaning particles 418 may be greater than the height of the seeds 419. The cleaning particles 418 may have a greater horizontal length L than the seeds 419. 1 and vertical length L 2 and a higher height T. The horizontal length L of the hexahedral cleaning particle 418 1 and vertical length L 2 The horizontal length L of the cleaning particles 418 may be about 20 μm to about 200 μm, and the height T of the cleaning particles 418 may be about 1 μm to about 10 μm. 1 and vertical length L 2 The height T of the cleaning particle 418 may be about 30 μm, respectively. The height T of the cleaning particle 418 may be about 5 μm. In an embodiment, the cleaning particle 418 may be a cube. In this case, the height T of the cleaning particle 418 may be equal to the horizontal length L of the cleaning particle 418. 1 and vertical length L 2 same.

[0082] Fig.12 A graph presenting the conductivity of the chemical solution 134 at a second temperature (610) and the conductivity of the chemical solution 134 at ambient temperature (620) is shown.

[0083] Reference Fig.12 , the conductivity (610) of the chemical solution 134 at the second temperature (e.g., a temperature of about 18°C) can decrease faster than the conductivity (620) of the chemical solution 134 at the ambient temperature (e.g., a temperature of about 20°C). Once the chemical solution 134 cools, the cleaning particles 418 can grow quickly from the seeds 419. If the chemical solution 134 is maintained at the first temperature of, for example, 26°C for about two hours, the seeds 419 may not grow into the cleaning particles 418.

[0084] Refer again Fig.10 , the controller 700 may determine whether the conductivity of the chemical solution 134 is saturated (e.g., whether the conductivity of the chemical solution 134 will decrease) (S170). If the conductivity of the chemical solution 134 is not saturated, the controller 700 may perform steps S140, S150, S160, and S170 again. For example, the thermostat 600 may cool the chemical solution 134 to below the second temperature.

[0085] On the other hand, if the conductivity of the chemical solution 134 is saturated, the controller 700 can determine that the cleaning particles 418 have been generated. Once the conductivity of the chemical solution 134 is saturated, the cleaning particles 418 can be in a hexahedral or cubic shape. Then, the preparation of the chemical solution 134 is completed. Thereafter, the chemical solution 134 can be circulated in the cleaning solution circulator 430.

[0086] Fig.13 A graph presenting a change in the conductivity of the chemical solution 134 according to the concentration of the organic solvent in the chemical solution 134 is shown.

[0087] Reference Fig.13 , when the concentration of the organic solvent in the chemical solution 134 is about 0.28M to about 0.42M, the conductivity of the chemical solution 134 can be saturated within about one hour. For example, the conductivity (630) of the chemical solution 134 having an IPA concentration of about 0.28M can be saturated within about 40 minutes. If the concentration of the organic solvent in the chemical solution 134 is lower than about 0.28M, the cleaning particles 418 or seeds 419 will not be generated. For example, if the concentration of the organic solvent in the chemical solution 134 is too low, the cleaning particles 418 will not form a predetermined height T within about one hour. The conductivity (640) of the chemical solution 134 having an IPA concentration of about 0.42M can be saturated within about 60 minutes. If the concentration of the organic solvent in the chemical solution 134 is higher than about 0.42M, the cleaning particles 418 or seeds 419 will not be generated because the concentration of the organic solvent in the chemical solution 134 is high.

[0088] Fig.14The height T of the cleaning particles 418 is shown according to Figure 4 FIG. 4 is a graph showing changes in the pressure of the chemical solution 134 in the circulation line 450 and the pump 460.

[0089] Reference Fig.14 , the height T of the cleaning particles 418 may be proportional to the pressure of the chemical solution 134. For example, when the pressure of the chemical solution 134 is 0 KPa, the cleaning particles 418 may have a height T of about 1 μm or less, and may have a horizontal length L of about 1 μm. 1 and vertical length L 2 In an embodiment, the cleaning particles 418 may have a horizontal length L of about 26 μm. 1 and vertical length L 2 When the pressure of the chemical solution 134 is 100 KPa, the cleaning particles 418 may have a height T of about 3 μm and a horizontal length L of about 10 μm. 1 and vertical length L 2 When the pressure of the chemical solution 134 is 200 KPa, the cleaning particles 418 may have a height T of about 5 μm. When the pressure of the chemical solution 134 is 200 KPa, the cleaning particles 418 may have a hexahedral shape.

[0090] Refer again Figure 4 and Fig. 9 , the cleaning device 130 may clean the substrate W using the chemical solution 134 (S200). The substrate W may be cleaned with a particle removal efficiency of about 80% or more.

[0091] The drying device 140 may dry the chemical solution 134 (S300). The first deionized water 132 and / or the chemical solution 134 may be removed from the substrate W.

[0092] By summarizing and reviewing, the cleaning process can remove process particles that can contaminate fine patterns. Standard Clean 1 (SC-1) solution is widely used as an etchant in the cleaning process. SC-1 solution may contain, for example, ammonia and hydrogen peroxide. SC-1 solution can remove process particles by providing a repelling force after surface etching. SC-1 solution can cause film loss due to surface etching.

[0093] Embodiments may provide a cleaning composition and an apparatus capable of easily washing away fine process particles, and a method of manufacturing a semiconductor device using the cleaning composition and the apparatus.

[0094] According to the above and other exemplary embodiments of the present disclosure, a cleaning composition including a hexadecyl ammonium sulfate surfactant and cleaning particles can be provided. The cleaning particles can adsorb and remove fine process particles from a substrate. The cleaning composition can provide excellent cleaning capabilities for removing fine process particles compared to a standard clean 1 (SC-1) solution.

[0095] Embodiments may provide a cleaning composition and a cleaning apparatus for removing process particles, and a method of manufacturing a semiconductor device using the cleaning composition and the cleaning apparatus.

[0096] Example embodiments have been disclosed herein, and although specific terms are employed, they are used and interpreted in a general and descriptive sense only, and not for limiting purposes. Taking into account measurement issues and errors associated with the measurement of specific quantities (i.e., limitations of the measurement system), "about" as used herein includes the stated values ​​and means within the acceptable deviation range of the specific value as determined by a person of ordinary skill in the art. For example, "about" can mean within one or more standard deviations, or within ±30%, ±20%, ±10%, ±5% of the stated value. In some cases, as will be apparent to a person of ordinary skill in the art since the filing of this application, unless otherwise specifically stated, the features, characteristics and / or elements described in conjunction with a particular embodiment may be used alone or in combination with the features, characteristics and / or elements described in conjunction with other embodiments. Therefore, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention as set forth in the claims.

Claims

1. A method for cleaning a substrate, the method comprising: The following steps are involved: preparing a cleaning solution, wherein the cleaning solution comprises a surfactant, deionized water and an organic solvent; Use a cleaning solution to clean the substrate; as well as Dry the substrate, The step of preparing the cleaning solution includes: providing deionized water into a chemical tank; generating the cleaning solution by mixing the organic solvent and the surfactant in the deionized water; generating seeds of cleaning particles formed by molecular arrangement of the surfactant by heating the cleaning solution to a first temperature; detecting the conductivity of the cleaning solution; and determining whether the seeds have been generated based on the detected conductivity of the cleaning solution. wherein the surfactant is included in the cleaning solution at a concentration of 0.004M to 0.04M or a molar fraction of 0.0003 to 0.0004, wherein the organic solvent is included in the cleaning solution at a concentration of 0.28M to 0.42M, and Wherein, the surfactant is represented by the following formula 1: (R 1 -O) a -(R 2 -O) b -SO 3 NH 4 (1) Among them, in formula 1, a and b are both integers from 0 to 18, provided that a and b are not 0 at the same time. R 1 and R 2 are all substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms, substituted or unsubstituted alkylene groups having 1 to 18 carbon atoms, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, or substituted or unsubstituted arylene groups having 6 to 14 carbon atoms, and When a is 3 to 18, (R 1 -O) randomly or in segments, when b is 3 to 18, (R 2 -O) repeat randomly or in segments.

2. The method according to claim 1, in, The first temperature is about 26°C.

3. The method according to claim 1, in, The seeds are plate-shaped and have a thickness of 1 μm or less.

4. The method according to claim 1, in, The step of preparing the cleaning solution further includes growing cleaning particles from the seeds by cooling the cleaning solution to a second temperature, if the seeds have been produced, the second temperature being lower than the first temperature.

5. The method according to claim 4, in, The second temperature is about 18°C.

6. The method according to claim 4, in: The step of preparing the cleaning solution further includes determining whether the conductivity of the cleaning solution is saturated, and When the conductivity of the cleaning liquid is saturated, the cleaning particles have a hexahedral or cubic shape.

7. The method according to claim 4, in, The cleaning particles have a horizontal length and a vertical length of 20 μm to 200 μm and a thickness of 1 μm to 10 μm.

Images