A gas distribution apparatus and delivery system for semiconductor precursors

Abstract

The application discloses a kind of gas distribution device and gas phase conveying system for semiconductor precursor, it is related to semiconductor integrated circuit manufacturing equipment technical field.Gas distribution device includes a main body and multiple from main body outwardly extending flow guide pipe, the end of each flow guide pipe is provided with a gas outlet.Each gas outlet is configured so that the carrier gas ejected therefrom has both a first directional component in a direction toward the interior of an ampoule container below, which has an angle of 5° to 20° with the vertical central axis of the container, and a second directional component that rotates circumferentially around the vertical central axis of the container, which has a deflection angle of 30° to 60° with the radial direction of the container.The application greatly extends the mixing path of the carrier gas and the precursor vapor, eliminates the flow dead zone in the cavity and the air path short circuit, realizes the non-impact large-area tangential sweeping of the liquid surface, and controls the precursor vapor concentration fluctuation at the ampoule gas outlet within ≤3%.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor integrated circuit manufacturing equipment technology, and specifically relates to a gas distribution device for high-stability gas phase delivery of low vapor pressure liquid precursors in chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes, and an ampoule-type gas phase delivery system including the gas distribution device. Background Technology

[0002] In semiconductor manufacturing processes, thin film deposition technologies (such as CVD and ALD) are core processes for constructing micro and nanoelectronic devices. With the continuous improvement of wafer integration and the shrinking of feature sizes, extremely stringent requirements are placed on the concentration stability and throughput of precursor materials during vapor-phase transport. Taking low vapor pressure liquid precursors such as dicobalt hexacarbonyl tert-butylacetylene (CCTBA) used in advanced cobalt interconnect processes and tetra(ethylmethylamino)hafnium (TEMAHf) used in high-k dielectric processes as examples, the saturated vapor pressure of these precursors at room temperature (25°C) is typically below 1 Torr. Achieving high stability and high-throughput vaporization and transport over long periods during transport is a key technical challenge affecting thin film deposition uniformity and device yield.

[0003] In existing technologies, gas-phase delivery methods for ampoules (chemical source bottles) are mainly divided into two categories. The first category is bubbling delivery, where the inlet pipe is directly inserted below the liquid surface of the liquid precursor, and gas-liquid contact and vaporization are promoted by bubbling the carrier gas. However, the bubbling method has an inherent drawback: the generation and collapse of bubbles in the liquid can cause violent splashing of the liquid precursor, producing large-sized (tens to hundreds of micrometers) droplets. Once these droplets enter downstream gas pipelines and valves, they not only cause pipeline blockage and corrosion but also damage the uniformity and electrical properties of the deposited film as particulate contaminants. The second category is top-space purging delivery, where the carrier gas is only introduced into the free space above the liquid for sweeping purging, and the inlet pipe is not inserted below the liquid surface. However, due to the extremely low saturated vapor pressure of the low vapor pressure precursor, this method suffers from insufficient mass transfer driving force, low phase change and mixing efficiency, and small precursor carry-out and low throughput. More importantly, because the flow path of the carrier gas in the container cavity is short and disordered, its mixing with the vapor above the liquid surface is extremely uneven, resulting in significant fluctuations in the outlet concentration over time (typically ranging from 10% to 40%), which completely fails to meet the requirement of consistent precursor supply concentration for precision semiconductor thin film growth.

[0004] To address the aforementioned issues, prior art patent CN110475905A proposes an ampoule with a nozzle and multiple angled nozzles. In this prior art, the air inlet port of the container has a nozzle at the end inside the container, the nozzle having at least two angled nozzles configured to guide airflow within the ampoule cavity such that the airflow ejected from the nozzles is not perpendicular to the liquid surface in the ampoule. In this patent, the tilt direction of the nozzles is limited to a single tilt angle θ relative to the vertical direction, with an exemplary range of 2° to 25°. This solution, through a single-dimensional vertical tilt angle design, to some extent prevents the foaming and splashing problems caused by the jet directly impacting the liquid surface at a 90° vertical angle, representing a relatively advanced top-space sweeping delivery solution in the prior art.

[0005] However, after conducting in-depth analysis and computational fluid dynamics (CFD) simulation reproduction of the prior art, the inventors of this application discovered the following fundamental defects in the prior art: (i) The existing technology only considers and limits the tilt angle of the nozzle on the vertical section containing the vertical central axis of the container (i.e., the longitudinal anti-impact angle), without constraining or guiding the spray direction of the nozzle in the horizontal plane. In actual operation, the direction of the carrier gas jet ejected from each nozzle based solely on the vertical tilt angle in the horizontal plane is purely radial outward (i.e., the horizontal projection direction of each jet coincides with or is substantially coincident with the radial direction of the container). Since the nozzles are usually uniformly arranged circumferentially, the multiple purely radial outward jets collide and cancel each other out in the horizontal plane after leaving the nozzles, and cannot form any orderly rotating flow field structure in the container cavity.

[0006] (ii) Under this purely radial jet flow pattern, the main body of the jet rapidly deflects upward after impacting the inner wall of the container, flowing directly to the outlet at the top of the container, forming a severe "gas path short circuit"—a large amount of carrier gas is discharged from the container before it has fully contacted and mixed with the precursor vapor above the liquid surface. At the same time, a large area of ​​low-velocity or even stagnant flow dead zones are formed in the middle region and the bottom near-wall region of the container. In these dead zones, the gas renewal rate is extremely low, and the precursor can hardly be effectively carried out of the container.

[0007] (iii) The aforementioned disordered lateral flow field and gas path short-circuiting phenomenon together cause the outlet precursor vapor concentration to exhibit large-scale non-periodic fluctuations in the time dimension. The peak-to-peak amplitude of the concentration fluctuation is usually as high as 20% to 40%, and it cannot be effectively suppressed by adjusting the carrier gas flow rate or container temperature.

[0008] In summary, the key technical problem that urgently needs to be solved in the field of semiconductor precursor gas phase delivery is how to actively guide and control the injection direction of the carrier gas in the horizontal plane, based on the existing single-dimensional vertical tilt anti-impact design, to construct an orderly, large-scale circulating three-dimensional flow field in the ampoule container cavity, eliminate flow dead zones and gas path short circuits, so as to achieve long-term high stability output of the outlet precursor vapor concentration. Summary of the Invention

[0009] In view of the problems in the related technologies, the present invention proposes a gas distribution device and delivery system for semiconductor precursors to overcome the above-mentioned technical problems existing in the prior art.

[0010] To solve the above-mentioned technical problems, the present invention is achieved through the following technical solution: A gas distribution device for semiconductor precursors, for installation inside an ampoule container containing a liquid precursor, comprising: A main body having an internal airflow chamber, the airflow chamber having an air inlet for receiving carrier gas; Multiple guide tubes extend outward from the airflow chamber, and each guide tube has an air outlet at its end; Each of the air outlets is configured such that the carrier gas ejected from the air outlet simultaneously has the following spatial characteristics: (i) A first direction component toward the lower interior of the body, wherein the angle α between the jetting direction in which the first direction component is located and the vertical central axis of the body is 5° to 20°; (ii) A second direction component that rotates circumferentially about the vertical central axis of the body, wherein the deflection angle β between the direction of the second direction component and a radial direction extending radially outward from the center of the air outlet along the body is 30° to 60°.

[0011] As a preferred embodiment, the deflection angle β is 40° to 50°, more preferably 43° to 47°, and most preferably 45°. Within this preferred angle range, the ratio of tangential (circumferential) momentum to radial / vertical momentum achieves optimal balance, resulting in optimal spatial order, axisymmetry, and temporal stability of the formed spiral downward vortex.

[0012] As a further preferred embodiment, the ratio β / α of the deflection angle to the included angle ranges from 2.0 to 6.0, more preferably from 3.0 to 4.5. This ratio range reflects the ratio between the tangential rotational driving force and the downward diffusion driving force, and is a comprehensive control parameter for the morphology of the three-dimensional helical flow field.

[0013] As a preferred embodiment, the included angle (i.e., the angle corresponding to the first directional component mentioned above, also known as the vertical tilt angle) is 10° to 15°. Within this range, the vertical velocity component of the carrier gas jet has been sufficiently attenuated by diffusion before reaching the liquid surface, and the dynamic pressure upon reaching the liquid surface is insufficient to cause impact deformation or bubbling of the liquid surface, while maintaining sufficient airflow-liquid surface contact driving force.

[0014] As a preferred embodiment, the number of guide tubes is 2 to 6. The multiple guide tubes are preferably distributed at equal angular intervals along the circumference of the main body. As a further preferred embodiment, the number of guide tubes is 3, distributed at equal 120° angles along the circumference of the main body, or 4, distributed at equal 90° angles along the circumference of the main body. This symmetrical distribution at equal angles facilitates the generation of a uniform tangential driving force distribution along the circumference, promoting the formation of a highly axisymmetric three-dimensional helical flow field.

[0015] As a preferred embodiment, the inner diameter of each of the outlets is 0.4 mm to 0.8 mm, more preferably 0.5 mm to 0.6 mm. This range of outlet inner diameters allows for sufficient jet kinetic energy to drive large-scale swirling flow while keeping the total pressure drop of the system within a reasonable range permissible by semiconductor process equipment (typically ≤5 psi).

[0016] As a preferred embodiment, the guide tube extends outward and downward from the main body, and the inner flow channel of the guide tube has a tapering shape from the main body to the air outlet. This tapering flow channel design is beneficial for accelerating the carrier gas, reducing flow separation and eddy losses, and improving the utilization efficiency of the injection kinetic energy.

[0017] As a preferred embodiment, the main body and the guide tube are made of at least one highly corrosion-resistant material selected from 316L stainless steel, Hastelloy C-22 (UNSN06022), and Hastelloy C-276 (UNS N10276), and the inner flow channel surface of the guide tube is electrolytically polished to form a smooth surface with a surface roughness Ra ≤ 0.4 μm, preferably Ra ≤ 0.2 μm. This low surface roughness of the inner flow channel surface can effectively reduce the adsorption and decomposition residue of precursor vapor on the inner wall of the flow channel, extend the service life of the device, and ensure the long-term repeatability of the delivered concentration.

[0018] As a preferred embodiment, in the operating state where the carrier gas is ejected from each outlet via the airflow chamber and the guide pipe, the carrier gas ejected from each outlet collaboratively forms a three-dimensional spiral downward swirling flow field rotating around the vertical central axis of the ampoule container inside the ampoule container. Specifically, under the action of the three-dimensional spiral downward swirling flow field, the fluctuation range of the precursor vapor concentration at the outlet of the ampoule container does not exceed 3%. More preferably, the fluctuation range of the precursor vapor concentration at the outlet does not exceed 1.5%.

[0019] As a preferred embodiment, the second directional component of each of the air outlets is oriented such that the ejected carrier gas is away from the location of the air outlet of the ampoule container, so that the ejected carrier gas first spirals downward along the inner wall of the ampoule container, turns back in the bottom region of the container, and then rises along the central region to the air outlet.

[0020] As a preferred embodiment, the liquid precursor is at least one selected from the group consisting of dicobalt hexacarbonyl tert-butylacetylene (CCTBA), tetraethylmethylamino hafnium (TEMAHf), tetradimethylamino titanium (TDMAT), and tetraethylmethylamino zirconium (TEMAZr).

[0021] As a preferred embodiment, the gas distribution device is fixed to an air inlet cover assembly by means of threaded connection, welding or integral molding through the upper end of the main body, and the shape of the airflow chamber is a conical diffusion cavity that gradually expands downward from the air inlet end.

[0022] The present invention also proposes a semiconductor precursor gas phase delivery system, comprising: An ampoule container having an internal cavity for containing a liquid precursor; An air inlet cover assembly is sealed and installed at the top opening of the ampoule container, the air inlet cover assembly being provided with an air inlet and an air outlet; and The aforementioned gas distribution device is fixedly installed below the air inlet cover assembly, and the air inlet end of the airflow chamber of the main body is in fluid communication with the air inlet port.

[0023] Compared with the prior art, the present invention has the following beneficial effects: (1) A three-dimensional spiral downward ordered circulating flow field rotating around a vertical central axis is creatively constructed. In this invention, a deterministic tangential rotational angular momentum defined by a second directional component (deflection angle β, 30° to 60°) is introduced into the ampoule-type gas distribution device and spatially coordinated with the downward diffusion momentum defined by the first directional component (angle α, 5° to 20°). The carrier gas jets ejected from multiple guide tubes carry a unified rotational angular momentum and are superimposed and coupled within the container cavity to form a large-scale, stable, and ordered three-dimensional spiral downward swirling flow field. This flow field has a deterministic closed-loop streamline of "spiral downward → sweeping liquid surface → central reversal → spiral upward", which overcomes the fundamental defects of the prior art, such as the disordered transverse flow field of the carrier gas in the container cavity and the mutual collision and cancellation of multiple jets in the horizontal plane.

[0024] (2) The stability of precursor vapor concentration at the outlet is improved by orders of magnitude. Under the action of the three-dimensional spiral downward swirling flow field, the actual spiral flow path of the carrier gas in the container cavity is extended to 2 to 3 times that of the existing radial injection scheme, and the mixing path and mixing time of the carrier gas and precursor vapor are increased by orders of magnitude. The fluctuation range of precursor vapor concentration at the outlet of the ampoule container can be stably controlled within ≤3% during the steady-state operation stage, and within ≤1.5% under the optimal parameter combination conditions, which can meet the stringent requirements of precursor supply consistency for advanced process nodes of 5nm and below.

[0025] (3) It fundamentally eliminates the flow dead zone and gas path short circuit in the container cavity. By unifying the orientation of the second directional component of the carrier gas ejected from each outlet to the direction away from the outlet, the carrier gas is forced to spiral downward along the inner wall of the container. After completing the full sweep of the liquid surface, it naturally turns back in the central area at the bottom of the container, and then spirals upward along the central axis area to the outlet, ensuring that every portion of carrier gas entering the container effectively participates in the vaporization and mixing process of the precursor.

[0026] (4) It achieves impact-free, large-area, and flattened tangential sweeping of the liquid surface. The first directional component (angle α) ensures that the vertical velocity component of the carrier gas jet is sufficiently attenuated to a safe level that will not cause impact deformation of the liquid surface when it reaches the liquid surface; the second directional component (deflection angle β) imparts a tangential velocity component to the jet, enabling the carrier gas to contact the liquid surface in a large-area tangential sweeping manner parallel to the liquid surface. Throughout the entire working process, the liquid surface remains flat and stable, without producing impact pits with a depth exceeding 0.5 mm, or any destructive phenomena such as droplet splashing or bubbling; at the same time, the tangential sweeping method reduces the velocity boundary layer on the gas-liquid interface to a minimum, maximizing the convective mass transfer coefficient and phase change mass transfer efficiency, and taking into account both ultra-high transport stability and high transport throughput. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of the invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is a schematic diagram of the structure of a semiconductor precursor gas phase delivery system according to the present invention; Figure 2 This is a schematic diagram of the structure of a gas distribution device for semiconductor precursors according to the present invention; Figure 3 This is a side view of a gas distribution device for semiconductor precursors according to the present invention; Figure 4This is a top view of a gas distribution device for semiconductor precursors according to the present invention; Figure 5 This is a top view of the gas distribution device according to Embodiment 5 of the present invention.

[0029] Among them: 100-Ampoule container, 200-Gas distribution device, 10-Main body, 20-Guide tube, 30-Airflow chamber, 201-Air outlet, 300-Air inlet cover assembly, 301-Air inlet pipe, 302-Air outlet pipe. Detailed Implementation

[0030] The technical solutions of the embodiments of the invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the invention, and not all embodiments. Based on the embodiments of the invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the invention.

[0031] In the description of this invention, it should be understood that the terms "opening", "upper", "lower", "top", "middle", "inner", etc., which indicate orientation or positional relationship, are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the components or elements referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the invention.

[0032] In the following embodiments, unless otherwise specified, the ampoule container 100 is a cylindrical container with an inner diameter of 80 mm and an internal total height of 150 mm; the initial filling amount of the liquid precursor (based on CCTBA, its saturated vapor pressure at 25°C is approximately 0.35 Torr) is 40% of the total internal volume of the container, that is, the initial liquid level is approximately 60 mm from the bottom of the container; the carrier gas (He) inlet flow rate is 100 sccm (standard state milliliters / minute), and the inlet temperature is consistent with the container set temperature; the container wall temperature is set as a constant wall temperature boundary condition.

[0033]

Example 1

[0034] The ampoule container 100 in this embodiment is a generally cylindrical, pressure-resistant, sealed container made of 316L stainless steel, designed to withstand a pressure of not less than 1000 psi, and used to contain a liquid precursor (in this embodiment, CCTBA is used as an example, with a molecular weight of 446.20 g / mol, a dark red liquid at room temperature, and a saturated vapor pressure of approximately 0.35 Torr at 25°C). An air inlet cover assembly 300 is sealed at the top opening of the ampoule container 100, and the air inlet cover assembly 300 is sealed to the ampoule container 100 by a metal gasket. An air inlet port 301 and an air outlet port 302 are provided through the air inlet cover assembly 300, with a center-to-center distance of 30 mm between the two ports.

[0035] The gas distribution device 200 of the present invention is fixedly installed below the air inlet cover assembly 300. The gas distribution device 200 includes a main body 10 and three guide pipes 20 extending outwards and downwards from the interior of the main body 10. The main body 10 is cylindrical with a hemispherical bottom, and an airflow chamber 30 is formed inside. The air inlet end of the airflow chamber 30 is sealed and connected to the air inlet port 301 to receive externally supplied carrier gas. The airflow chamber 30 is a tapered diffusion cavity that gradually expands downwards from the air inlet end, with an inner diameter of 4 mm at the air inlet end and an inner diameter that expands to 12 mm at the bottom. This tapered expansion design is used to reduce the local flow velocity of the carrier gas when it enters the main body 10, allowing the airflow to fully develop and obtain a uniform pressure distribution before being diverted into the three guide pipes 20, thereby ensuring the consistency of the outlet flow rate of the three outlets 201.

[0036] Three guide pipes 20 are evenly distributed at 120° angles around the circumference of the main body 10. The inner flow channel of each guide pipe 20 tapers in a gradually narrowing shape from the main body 10 to the outlet 201—the inner diameter of the guide pipe 20 at the connection with the main body 10 is 3mm, gradually narrowing to 0.5mm at the outlet 201, thereby accelerating the carrier gas as it flows through the guide pipe 20. The main body 10 and the three guide pipes 20 are integrally formed from 316L stainless steel through five-axis CNC precision machining, and then the inner surface of the flow channel is electrolytically polished to a surface roughness Ra≤0.2μm. The integral molding design completely eliminates the risk of dead space and particulate residue at the welded joints.

[0037] like Figure 3 As shown, in the vertical projection plane where each air outlet 201 is located and is coplanar with the vertical central axis of the main body 10, the angle α between the jet center axis of the air outlet 201 and the vertical central axis of the main body 10 is 12° in this embodiment.

[0038] like Figure 4As shown, in this horizontal projection plane, the deflection angle β between the horizontal projection line of the jet direction of the air outlet 201 and the radial direction extending outward along the body 10 with the center of the air outlet 201 as a reference is 45° in this embodiment.

[0039] In operation, the carrier gas (in this embodiment, high-purity helium (He) with a purity of 99.9999% and an inlet flow rate of 100 sccm) enters the airflow chamber 30 of the main body 10 through the inlet 301. After being decelerated and pressurized in the conical diffusion chamber, it is split into three guide pipes 20. The carrier gas is accelerated in the gradually narrowing inner flow channels of the three guide pipes 20 and ejected as high-speed jets from three outlets 201 with an inner diameter of 0.5 mm. Since each outlet 201 has both an included angle α = 12° (downward component) and a deflection angle β = 45° (tangential rotational component) in space, the three high-speed carrier gas jets ejected from each outlet 201 simultaneously possess downward diffusion momentum toward the liquid surface at the bottom of the container and tangential angular momentum around the vertical central axis of the container in the same rotational direction (clockwise in this embodiment). The three jets generated by the three 120° symmetrically distributed outlets 201 have the same tangential angular momentum direction—all in a clockwise rotation direction—and therefore superimpose and synergistically enhance each other within the container cavity, rather than canceling each other out. After leaving the outlets 201, the three jets rapidly converge and merge, jointly driving the gas inside the ampoule container 100 to form a uniform, highly axisymmetric, three-dimensional spiral downward swirling flow.

[0040] The three-dimensional spiral downward swirling flow adheres to the inner cylindrical wall of the ampoule container 100 under inertia, descending steadily along a helical trajectory. The pitch of the downward spiral is approximately 25 mm to 30 mm in the upper part of the container (closer to the outlet 201), gradually increasing to approximately 40 mm to 50 mm near the liquid surface as the airflow moves downward and momentum dissipates along the path. When the airflow reaches the liquid surface, the vertical velocity component is sufficiently attenuated due to the angle α. Because the vertical impact dynamic pressure of the airflow is extremely small throughout the sweeping process (dynamic pressure < 5 Pa, far below the critical dynamic pressure of approximately 50 Pa that the surface tension of the CCTBA liquid surface can withstand), the liquid surface remains flat and stable throughout the entire working process, without any observable pitting deformation, droplet splashing, or bubble formation.

[0041] After the tangential sweep of the liquid surface is completed, the mixed gas, which carries a large amount of CCTBA vapor (at a container temperature of 40°C, the molar fraction of CCTBA at the outlet is approximately 0.005 to 0.015), undergoes natural flow reversal in the bottom central region of the ampoule container 100 due to geometric constraints. The reversed mixed gas rises along the central axis region of the container in a spiral trajectory and is finally output from the outlet 302 located at the top of the container to the downstream semiconductor thin film deposition process chamber (such as the ALD cobalt interconnect deposition chamber).

[0042] In this embodiment, the lowest position of the opening end of the gas outlet 302 inside the ampoule container 100 is vertically higher than the positions of the three gas outlets 201 of the gas distribution device 200, with a vertical distance of 30mm between them. This ensures that the mixed gas flow rising from the liquid surface must complete a full cycle of spiral descent → sweeping the liquid surface → central reversal → spiral ascent before its top reaches the height of the opening end of the gas outlet 302. This avoids the possibility of carrier gas that has not fully participated in the vaporization of the precursor "taking a shortcut" and directly entering the gas outlet 302.

[0043] Experiments show that a clearly identifiable three-dimensional spiral downward flow field structure is formed within the 100-cavity ampoule container. The upper pitch of the spiral flow field is approximately 30mm to 35mm, the actual spiral stroke of the airflow is approximately 480mm, and the low-velocity dead zone accounts for approximately 2%. The liquid surface remains flat and stable throughout the entire operating process, without any observable pitting deformation, droplet splashing, or bubble formation. The maximum pit depth is <0.2mm. During the steady-state operation period of 50s to 300s, the CCTBA vapor concentration at the outlet fluctuates between 1% and 1.5%.

[0044]

Example 2

[0045] Experiments show that, under this parameter combination, a clearly identifiable three-dimensional spiral downward flow field structure is still formed within the ampoule container 100. However, due to the relative reduction in tangential rotational driving force, the pitch of the spiral flow field is larger than that of Example 1 (the upper pitch is approximately 35 mm to 40 mm), and the actual spiral stroke of the airflow is approximately 380 mm—significantly longer than the prior art (approximately 200 mm for radial injection), but shorter than approximately 480 mm in Example 1. The low-velocity dead zone accounts for approximately 5%. During steady-state operation from 50 s to 300 s, the CCTBA vapor concentration at the outlet fluctuates between 2.3% and 2.8%.

[0046]

Example 3

[0047] Experiments show that under this parameter combination, due to the significantly enhanced tangential rotational driving force, the airflow adheres almost immediately to the inner wall of the container after leaving the outlet 201. The wall adhesion of the spiral downward flow field is very strong, with a small pitch (approximately 18 mm to 22 mm at the top), and the actual spiral stroke of the airflow is the longest, reaching approximately 550 mm. However, the strong tangential rotation also leads to relatively limited radial diffusion of the airflow, resulting in a relatively low airflow velocity in the central region of the container (within a radius of 15 mm from the central axis) during the spiral downward phase. When the airflow turns back at the bottom, the rising airflow velocity in the central region is also correspondingly low, with a low-velocity dead zone accounting for approximately 5%. During the steady-state operation period of 50 to 300 s, the CCTBA vapor concentration at the outlet fluctuated between 1.8% and 2.6%.

[0048]

Example 4

[0049] Since only two outlets 201 generate tangential driving force, compared to the more uniform circumferential driving force generated by three outlets distributed at 120° in Example 1, the circumferential driving force in this example exhibits a spatially spaced distribution of 180° intervals, resulting in slightly reduced symmetry. Experiments show that the tangential momentum generated by the two outlets 201 is fully diffused and circumferentially homogenized after approximately half a rotation within the container cavity. Therefore, near the liquid surface height, the circumferential homogeneity of the spiral downward flow field is comparable to that of Example 1, with a low-velocity dead zone accounting for approximately 8%. During steady-state operation from 50s to 300s, the CCTBA vapor concentration at the outlet fluctuated between 2.0% and 3.5%.

[0050]

Example 5

[0051] Because the four outlets 201 provide tangential driving force with a higher spatial density, the circumferential uniformity of the three-dimensional spiral downward flow field within the container cavity is slightly improved compared to Example 1 (3 outlets, distributed at 120°), the axisymmetry of the flow field is more ideal, and the low-velocity dead zone accounts for approximately 1.5%. During steady-state operation from 50 s to 300 s, the CCTBA vapor concentration at the outlet fluctuated between 1.2% and 1.8%.

[0052]

Example 6

[0053]

Comparative Example 1

[0054]

Comparative Example 2

[0055] Experiments show that the high-speed jet creates a distinct impact pit exceeding 3 mm in depth on the liquid surface. The liquid at the edge of the pit is torn and peeled off by the shearing action of the high-speed airflow, forming numerous droplets ranging in diameter from several micrometers to hundreds of micrometers. These droplets are carried by the carrier gas into the outlet 302, posing a serious risk of particulate contamination to the downstream semiconductor thin-film deposition process chamber. The strong impact of the jet on the liquid surface causes violent oscillations and localized bubble generation and collapse. The droplets released during bubble collapse further exacerbate the droplet phenomenon. Because the jets are all vertically downward, the carrier gas bounces and diffuses randomly above the liquid surface after impact, creating an extremely turbulent flow field within the container cavity. There is no ordered flow structure within the entire container cavity, with low-velocity dead zones accounting for 15% to 25%. During the steady-state operation period of 50 to 300 seconds, the CCTBA vapor concentration at the outlet fluctuates by 35% to 60%.

[0056] Table 1 Comparison of CFD simulation results for different schemes ; In the table, "spiral stroke" is defined as the total length of the three-dimensional spatial trajectory traversed by the carrier gas from the outlet 201 to the height at which it first reaches the outlet 302. This is calculated by averaging the trajectory lengths of 50 massless tracer particles using the particle tracking function in CFD post-processing. "Dead zone percentage" is defined as the percentage of the volume of the region inside the container where the average gas residence time exceeds 10 seconds, relative to the total volume of the gas inside the container. "Outlet concentration fluctuation" is defined as the percentage deviation of the maximum value of the precursor vapor mole fraction at the outlet 302 cross-section from the average value during steady-state operation (50s to 300s).

[0057] As can be clearly seen from Table 1: (1) The spiral stroke of Comparative Examples 1 and 2 is only about 200 mm, the dead zone accounts for as high as 35% to 45%, and the outlet concentration fluctuates as high as 20% to 40%, reflecting the fundamental defects of the existing technical solutions.

[0058] (2) By introducing a second directional component (deflection angle β, 30° to 60°), all embodiments of the present invention achieve a significant extension of the spiral stroke (380 mm to 550 mm), a significant reduction in the dead zone ratio (<8%, optimal <2%), and an order of magnitude reduction in the outlet concentration fluctuation (≤3.5%, optimal ≤1.5%).

[0059] (3) Based on the comprehensive data from Examples 1 to 6, it can be concluded that the optimal range of the deflection angle β can be further preferred to be 40° to 50° (β / α≈3.3 to 4.2), within which the outlet concentration fluctuation does not exceed 3%. The inner diameter of the outlet 201 has a relatively mild impact on the system performance—when the inner diameter increases from 0.5 mm to 0.8 mm, the outlet concentration fluctuation slightly increases from ≤1.5% to 2.5% to 3.5%, indicating that the inner diameter of the outlet 201 has a good process window in the range of 0.4 mm to 0.8 mm.

[0060] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0061] The preferred embodiments of the invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A gas distribution device for semiconductor precursors, for installation inside an ampoule containing a liquid precursor, characterized in that, include: A main body having an internal airflow chamber, the airflow chamber having an air inlet for receiving carrier gas; Multiple guide tubes extend outward from the airflow chamber, and each guide tube has an air outlet at its end; Each of the air outlets is configured such that the carrier gas ejected from the air outlet simultaneously has the following spatial characteristics: (i) A first direction component toward the lower interior of the body, wherein the angle α between the jetting direction in which the first direction component is located and the vertical central axis of the body is 5° to 20°; (ii) A second direction component that rotates circumferentially about the vertical central axis of the body, wherein the deflection angle β between the direction of the second direction component and a radial direction extending radially outward from the center of the air outlet along the body is 30° to 60°.

2. The gas distribution device according to claim 1, characterized in that, The deflection angle β is 40° to 50°, and the included angle α is 10° to 15°.

3. The gas distribution device according to claim 1, characterized in that, The ratio β / α of the deflection angle to the included angle ranges from 2.0 to 6.

0.

4. The gas distribution device according to claim 1, characterized in that, The multiple guide tubes are distributed at equal angular intervals in the circumferential direction of the main body.

5. The gas distribution device according to claim 1, characterized in that, The inner diameter of each of the air outlets is 0.4 mm to 0.8 mm.

6. The gas distribution device according to claim 1, characterized in that, The guide tube extends outward and downward from the main body, and the inner flow channel of the guide tube has a gradually narrowing shape in the direction from the main body to the air outlet.

7. The gas distribution device according to any one of claims 1 to 6, characterized in that, When the carrier gas is ejected from each outlet through the airflow chamber and the guide pipe, the carrier gas ejected from each outlet cooperates to form a three-dimensional spiral downward swirling flow field rotating around the vertical central axis of the ampoule container inside the ampoule container.

8. The gas distribution device according to any one of claims 1 to 6, characterized in that, The second directional component of each of the air outlets is oriented such that the ejected carrier gas is away from the location of the air outlet of the ampoule container, so that the ejected carrier gas first spirals downward along the inner wall of the ampoule container, turns back in the bottom region of the container, and then rises along the central region to the air outlet.

9. The gas distribution device according to any one of claims 1 to 6, characterized in that, The main body and the guide tube are made of at least one material selected from 316L stainless steel, Hastelloy C-22, and Hastelloy C-276, and the inner flow channel surface of the guide tube has a smooth surface with a surface roughness Ra≤0.4μm formed by electrolytic polishing.

10. A semiconductor precursor vapor phase delivery system, characterized in that, include: An ampoule container having an internal cavity for containing a liquid precursor; An air inlet cover assembly is sealed and installed at the top opening of the ampoule container, and the air inlet cover assembly is provided with an air inlet and an air outlet. as well as According to any one of claims 1 to 9, the gas distribution device is fixedly installed below the air inlet cover assembly, and the air inlet end of the airflow chamber of the main body is in fluid communication with the air inlet port.

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