| HS Code | 128669 |
| Product Name | Hydrochloric Acid-Hydrogen Peroxide Mixture (HPM) |
| Grade | Electronic/EL Grade |
| Chemical Composition | Aqueous acidic oxidizing mixture of hydrogen chloride (HCl) and hydrogen peroxide (H2O2) |
| Component Cas Numbers | HCl: 7647-01-0; H2O2: 7722-84-1; H2O: 7732-18-5 |
| Typical Formulation | HCl:H2O2:H2O = 1:1:5 by volume |
| Typical Working Concentration | Approximately 5-6% HCl, 4-5% H2O2, balance high-purity water |
| Appearance | Clear, colorless liquid |
| Physical State | Liquid at normal room temperature |
| Odor | Pungent, sharp, acidic odor |
| Ph | Strongly acidic; pH less than 1 |
| Specific Gravity | Approximately 1.03-1.05 at 20°C |
| Boiling Point | No single sharp boiling point; about 100°C with decomposition and oxygen evolution upon heating |
| Freezing Point | Approximately 0°C |
| Vapor Pressure | Approximately 2.3 kPa at 20°C; close to that of water |
| Solubility | Fully miscible with water in all proportions |
| Stability | Stable under cool, clean, and uncontaminated storage; decomposes when heated or exposed to transition-metal impurities |
| Decomposition Products | Oxygen gas, water, hydrogen chloride, and chlorine-related species |
| Oxidizing Properties | Strong oxidizer due to hydrogen peroxide and corrosive acidic properties due to hydrochloric acid |
| Incompatibility | Incompatible with reducing agents, strong alkalis, heavy-metal catalysts, organic compounds, and many base metals |
As an accredited Hydrochloric Acid-Hydrogen Peroxide Mixture (HPM) Electronic/EL Grade factory, we enforce strict quality protocols—every batch undergoes rigorous testing to ensure consistent efficacy and safety standards.
| Packing | Supplied in 1-gallon (3.8 L) high-purity HDPE bottles, nitrogen-purged and sealed to maintain electronic/EL grade cleanliness. |
| Container Loading (20′ FCL) | Load drums/IBCs of HPM into 20′ FCL, securely braced, segregated from combustibles, with ventilated container and proper DG placarding. |
| Shipping | UN 3149, Hydrogen Peroxide and Hydrochloric Acid Mixture, Electronic/EL Grade, Class 5.1 (8), Packing Group II. Ship in PTFE or high-purity HDPE-lined containers with vented closures, inside clean, robust outer packaging. Segregate from combustibles, reducing agents, alkalis, and metal powders; keep cool and ventilated. Label as Oxidizer and Corrosive. |
| Storage | Store HPM (Electronic/EL Grade) in tightly sealed, high-purity containers made of PTFE, PFA, or quartz-lined materials. Keep in a cool, well-ventilated, acid-cabinet area away from direct sunlight, heat, and incompatible substances such as organic materials, bases, and reactive metals. Use secondary containment and ensure no contamination or contact with metal surfaces. |
| Shelf Life | Shelf life is typically 6 months from manufacture if stored unopened, tightly sealed, in original containers at controlled temperature away from light. |
In 300 mm logic and memory wafer fabrication, post-SC-1 metal contamination on silicon wafer surfaces prior to gate dielectric deposition is reduced by RCA SC-2 treatment using electronic/EL-grade HPM. The mixture is blended at point of use from hydrochloric acid conforming to SEMI C27 and hydrogen peroxide conforming to SEMI C35, together with ultrapure water, at volumetric ratios of 6:1:1 or 5:1:1 H2O:HCl:H2O2. The quartz or PFA-lined bath is held at 75 °C to 80 °C and wafer immersion lasts 10 min to 12 min. Under these conditions the peroxide oxidizes residual Fe, Cu, Zn, Ni, and Ca species while the chloride anion forms soluble chloro-complexes; TXRF analysis on monitor wafers records metallic surface densities below 5 × 10^10 atoms/cm² when incoming contamination is below 1 × 10^12 atoms/cm². Peroxide decomposition at 80 °C proceeds at 0.3 wt% to 1.0 wt% per hour, so the recirculation loop is operated at 0.5 to 1.0 bath volumes per minute and the concentration is checked by titration every 4 h. The terminal product of this step is a silicon surface with controlled metal contamination for high-k gate stack deposition, DRAM capacitor formation, and 3D NAND slit patterning; after the HPM treatment, wafers enter an overflow rinse with UPW of resistivity not less than 18.2 MΩ·cm to remove chloride residues before spin drying.
| Control variable | Set point or range | Monitoring instrument |
|---|---|---|
| Volumetric ratio H2O:HCl:H2O2 | 5:1:1–6:1:1 | Mass-flow controller calibration |
| Bath temperature | 75 °C–80 °C | PFA-sheathed PT100 sensor |
| Immersion time | 10 min–12 min | Automated wafer transfer |
| Liquid particle count ≥ 0.2 µm | ≤ 100 counts/mL | SEMI C15 optical particle counter |
| Final UPW rinse resistivity | ≥ 18.2 MΩ·cm | ASTM D5127-13 Type E-1 |
Wet mesa etching of InP-based edge-emitting lasers, electroabsorption modulators, and PIN photodetectors uses HCl-H2O2-H2O mixtures because hydrogen peroxide moderates the otherwise fast HCl attack on InP. A starting blend of 1:1:2 HCl:H2O2:H2O at 25 °C is introduced to single-wafer immersion or spray tools; the solution is used within 2 h after blending because the etch rate drifts as peroxide decomposes. Published etch-rate data for this specific configuration is limited, and production qualification normally relies on blanket InP wafers measured by stylus profilometry and scanning electron microscopy. Increasing the H2O2 fraction by 1 volume relative to HCl shifts the surface reaction toward oxide formation and reduces InP removal, while lowering the H2O2 fraction produces a chloride-dominated etch with higher surface roughness. Temperature control must be maintained within ±0.5 °C, and the short bath life is confirmed by titration of the remaining peroxide concentration. The finished mesa structure is used for 1.3 µm and 1.55 µm distributed-feedback lasers and avalanche photodiodes; a deionized water quench and nitrogen spin dry terminate the etch and prevent post-etch oxidation of the exposed InP sidewalls. Production-scale failure modes include local etch-depth non-uniformity across a 2-inch wafer when the spray bar temperature differs by more than 5 °C from the bath setpoint and formation of crystalline precipitates when the solution age exceeds 4 h. The HPM mixture is filtered through 0.2 µm PFA filters immediately before use, and the etch cell is exhausted to remove chlorine species released under high peroxide loading.
Post-CMP cleaning of copper/low-k damascene structures uses dilute HPM when benzotriazole-copper complexes and residual slurry particles must be removed without roughening the copper surface beyond 10 nm RMS. The point-of-use mixture is 1:1:10 HCl:H2O2:H2O at 25 °C to 30 °C, dispensed for 30 s to 60 s in a single-wafer spray tool with wafer rotation between 20 rpm and 40 rpm. Atomic force microscopy on 90 nm node copper arrays shows root-mean-square roughness increases below 0.3 nm when contact time is held below 60 s; longer exposure accelerates copper dissolution at grain boundaries and increases line-edge roughness beyond 1.0 nm. The chloride-peroxide mixture dissolves cupric oxide and cuprous chloride residue, but it will also attack exposed cobalt or ruthenium liners if the low-k dielectric barrier is breached. The clean is followed by UPW rinse conforming to ASTM D5127-13 Type E-1 and by a dilute organic acid passivation step to reduce chloride retention. The terminal wafers proceed to barrier/seed deposition for advanced logic interconnects; process release criteria include TXRF chloride below 1 × 10^13 atoms/cm² and surface roughness measured by AFM on a monitor die at the wafer edge.
In HDI PCB manufacturing, copper foil is microetched with HCl-H2O2-H2O before dry-film lamination or liquid photoimageable solder mask coating to increase mechanical adhesion and remove chromate residues from prior surface treatment. The horizontal spray module operates at 35 °C to 40 °C, and the conveyor speed is set to remove 1 µm to 3 µm of copper. Spray pressure of 1.5 bar to 2.5 bar and nozzle spacing of 50 mm to 80 mm produce etch uniformity of ±0.3 µm across a panel width of 500 mm. The bath is regenerated by the cupric chloride mechanism, in which hydrogen peroxide oxidizes cuprous ions back to cupric ions and hydrochloric acid supplies chloride for continued copper dissolution. Process control relies on titration of free chloride and cupric ion concentration; when cupric concentration exceeds 80 g/L, the etch becomes diffusion-limited and non-uniform. The treated copper foil is used for 5G smartphone main boards, chip-on-board modules, and high-density multilayer packages; after lamination, peel strength is tested per IPC-TM-650 method 2.4.8 with acceptance depending on the laminate grade and foil profile.
For 300 mm wafer cleaning tools, electronic/EL-grade HPM is generated at the point of use by blending 36.5–37.0 wt% HCl conforming to SEMI C27, 30.0–31.0 wt% H2O2 conforming to SEMI C35, and UPW conforming to ASTM D5127-13 Type E-1. The static mixer residence time is held below 2 s at 20 °C to 25 °C to limit adiabatic temperature rise and peroxide decomposition; downstream filtration through 0.1 µm PFA or PTFE membrane cartridges removes particles introduced by valves and fittings. Blend accuracy of ±1% of setpoint is maintained by Coriolis mass-flow meters on each chemical line, and conductivity sensors provide closed-loop feedback to the control panel. A degassing membrane removes oxygen released by peroxide decomposition, while a pressure-relief valve set at 3 bar protects the dispense line. All wetted components are unpigmented PFA, PTFE, or quartz to minimize trace metal extraction; ICP-MS analysis of the blended output is performed at installation and after preventive maintenance to verify cation levels against SEMI C35 specifications. This delivery mode supports single-wafer spray tools and batch immersion tools in advanced logic and memory fabs while avoiding the etch-rate drift observed when mixed HPM is aged in intermediate storage tanks.
| Input stream | Standard or specification | Critical control parameter | Acceptance range |
|---|---|---|---|
| Hydrochloric acid | SEMI C27 | Assay | 36.5–37.0 wt% |
| Hydrogen peroxide | SEMI C35 | Assay | 30.0–31.0 wt% |
| Ultrapure water | ASTM D5127-13 Type E-1 | Resistivity | ≥ 18.2 MΩ·cm |
| Blended HPM | Point-of-use filtered | Liquid particle count ≥ 0.2 µm | ≤ 100 counts/mL |
For quartz diffusion tubes, wafer boats, and thermocouple sheaths in LPCVD and annealing furnaces, trace metal contamination is reduced by immersion reconditioning in electronic/EL-grade HPM. Quartz parts are immersed in a 1:1:5 HCl:H2O2:H2O mixture at 70 °C to 80 °C for 15 min to 20 min in a dedicated quartz tank, followed by an overflow rinse with hot UPW conforming to ASTM D5127-13 Type E-1 for 10 min. The mixture dissolves surface metal oxides and alkali residues without measurable quartz attack; fused silica etch loss is below 0.5 nm/min at 75 °C. Reconditioned quartzware is dried in an ISO 14644-1:2015 Class 4 cleanroom oven and tested by TXRF for Fe, Ca, Cu, and Ni before return to production. Production-scale failure modes occur when the bath is not completely exchanged after 8 h or when the peroxide concentration falls below 50% of its initial value, allowing metal redeposition on the ware and cross-contamination of subsequent furnace runs. This reconditioning process is also applied to compatible silicon carbide and silicon nitride process carriers after acidic cleaning compatibility verification.
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Hydrochloric Acid-Hydrogen Peroxide Mixture (HPM) Electronic/EL Grade is supplied as a pre-blended or point-of-use diluted acidic peroxide solution for semiconductor wet-bench and single-wafer cleaning. The mixture is defined by the volumetric ratio of hydrochloric acid (35–37% w/w HCl), hydrogen peroxide (30–31% w/w H2O2), and ultrapure water. Common production dilution ratios include 1:1:5, 1:1:6, and 1:1:10, expressed as HCl:H2O2:UPW. Product codes are manufacturer-specific and typically encode blend ratio, packaging size, and packaging polymer; no universal model designation applies across suppliers. In semiconductor manufacturing the solution is used primarily for metallic contaminant removal after dry etch, resist ash, and wet etch operations, and for selective metal residue control where low silicon dioxide etch rates are required. The electronic/EL grade designation imposes trace-metal, particulate, and anion limits that are not present in technical-grade acid peroxide mixtures used for printed circuit board copper etching.
Acceptance criteria for the mixture combine the individual high-purity hydrochloric acid and hydrogen peroxide electronic-grade specifications with blend-specific stability data. For the hydrochloric acid component, supplier certificates of analysis commonly cite SEMI C28 for hydrochloric acid limits; the peroxide component is controlled under a corresponding high-purity peroxide specification such as SEMI C29. The pre-blended HPM release typically requires a minimum H2O2 assay before wafer processing, measured by potassium permanganate titration or ceric sulfate titration. Trace metal verification is performed by inductively coupled plasma mass spectrometry after acid dilution, with detection limits below 0.5 ppt for key transition metals in ultra-clean laboratories. Particle levels are measured by laser particle counters on samples after 30 min of recirculation through 0.1 µm polypropylene or PTFE filters.
Typical electronic/EL grade release limits are summarised below. These are not universal supplier specifications but represent commonly applied industry acceptance windows for front-end semiconductor cleaning.
| Parameter | Typical electronic/EL grade limit | Analytical method |
| HCl assay in concentrate | 35–37% w/w | acid-base titration |
| H2O2 assay in concentrate | 30–31% w/w; working bath typically 1.0–3.0% w/w | oxidation-reduction titration |
| Fe, Ni, Cu, Al, Zn per element | ≤5 ppb in each concentrate before blending | ICP-MS per EPA 6020B or equivalent |
| Na, K combined | ≤10 ppb | ICP-MS/OES |
| Particles ≥ 0.2 µm | ≤50 counts/mL after filtration | laser particle counter |
| Sulfate | ≤200 ppb | ion chromatography per ASTM D4327-17 |
| TOC in blended bath | ≤50 ppm | UV persulfate oxidation |
For advanced logic nodes, some manufacturers apply tighter metal and particle budgets than those shown, particularly when the bath is used before high-k/metal gate deposition.
In front-end-of-line wet cleaning, the HPM step is operated in recirculated immersion tanks fabricated from PTFE, PFA, or quartz with overflow weirs, megasonics, and point-of-use ultrapure water heating. The bath temperature is maintained between 65 °C and 80 °C, with a typical set point of 70 °C. In a DHF-last integration flow, the HPM step follows SC-1 cleaning and is used to remove alkali and transition metal contaminants; the H2O2 oxidises Fe2+ and other reduced metals, while HCl forms soluble chloride species that remain in the rinse. Single-wafer spray processors dispense the mixture through PFA nozzles at flow rates from 1.2 L/min to 2.0 L/min, often with nitrogen-purged chemical cabinets. On production lines, bath life is not defined by HCl depletion but by H2O2 decay and metal accumulation in the recirculation loop. Open-bath operation at 70 °C can exhibit H2O2 loss of 3–7% per hour when catalytic transition metals exceed 10 ppb; therefore replenishment is commonly controlled by oxidation-reduction potential or periodic peroxide titration rather than fixed time. Particle filters are replaced after each bath change, and filter housing materials must be PVDF or PTFE because HCl vapour degrades polycarbonate. Thermal silicon dioxide removal is typically less than 0.1 nm/min under these conditions; specific removal-rate values for high-k/metal gate structures are not fully disclosed in public literature, and published data for this specific configuration is limited.
HPM Electronic/EL Grade is applied to CF4/Cl2 plasma-etched aluminium and tungsten interconnect structures where residual metal chlorides and fluorine-containing residues must be removed without attacking low-temperature silicon dioxide or TiN diffusion barriers. The process is configured at 1:1:5 dilution and 65 °C to limit galvanic corrosion of Al-Cu alloy lines; the hydrogen peroxide concentration is kept at the lower end of the operating window to reduce oxygen evolution at the metal surface. On single-wafer tools, the chemical is dispensed onto the rotating wafer for 30–60 s, followed by ultrapure water rinse and spin-dry under nitrogen. The HCl component removes metal oxides; the H2O2 passivates exposed aluminium by forming a thin aluminium oxide layer, but the passivation thickness depends on peroxide concentration and electrochemical potential. Therefore the H2O2:HCl ratio is controlled by mass flow meters with a tolerance of ±5% on the peroxide concentrate line. A known production failure mode is the formation of aluminium hydroxide smut when the H2O2 concentration falls below 0.5% w/w in an aged bath; this has been observed on patterned wafers as a visible white residue after spin-drying. For tungsten structures, the same chemistry removes post-etch residues while tungsten recess is limited when the wafer is processed at 65 °C for 60 s. The bath is recirculated through 0.05 µm PTFE filters to control defect density after etch residue removal.
Substitution is not simply a purity upgrade; the electronic/EL product has a documented difference in stabilizer content, packaging metallisation, particulate cleanliness, and lot traceability. Technical-grade HCl/H2O2 mixtures used for copper etching or metal finishing often contain sulfate, iron, and organic additives, and are handled in HDPE drums that can leach zinc or calcium. In semiconductor use, those species increase surface recombination velocity and gate oxide defect density. The electronic/EL grade is packaged in fluoropolymer-lined or PFA containers, with lot-specific certificates that include per-lot ICP-MS data and particle counts. The table below summarises the practical gaps.
| Parameter | Technical-grade HPM (PCB/metal finishing) | Electronic/EL grade |
| Trace metal per critical element | 100 ppb–1 ppm, varies by lot | ≤5 ppb for Fe, Ni, Cu, Al, Zn |
| Particles ≥ 0.2 µm | not specified | ≤50 counts/mL |
| Stabilizers | may contain silicates, stannates, or organic inhibitors | no tin/antimony stabilizers; low-residue formulation |
| Packaging | HDPE or lined steel drums | PFA/fluoropolymer-lined drum or ISO container |
| Lot documentation | basic certificate of analysis | full semiconductor CoA with ICP-MS data, particle count, and anion profile |
| Application | bulk copper etching, metal finishing | semiconductor FEOL/BEOL cleaning and metal residue control |
| Use with exposed Cu/low-k structures | acceptable for PCB surface finishing | requires corrosion risk evaluation with benzotriazole or equivalent inhibitor |
The main operational consequence is bath life. Technical-grade baths may run until metal loading reaches gram-per-litre levels in etching applications; electronic-grade baths are replenished or changed when key metals exceed 10 ppb in the working bath, because even low-ppb contamination near gate oxide interfaces alters threshold voltage stability in high-k/metal gate devices. In addition, electronic/EL grade HPM is not interchangeable with SC-1 or SPM in the process sequence. SC-1 removes particulate and organic defects, SPM removes photoresist and heavy carbonaceous residues, and HPM removes metallic contaminant species; each chemistry has a distinct oxidation potential, pH range, and material compatibility boundary.
Storage and handling boundaries for HPM Electronic/EL Grade are determined by gas evolution and chloride corrosion. Pre-blended material is stored at 10–25 °C in vented, UV-shielded cabinets; sealed containers are prohibited because hydrogen peroxide decomposition releases oxygen and can pressurise. The product must be segregated from ammonia hydroxide, SC-1 baths, sulfuric acid, flammable solvents, and reducing agents. Equipment metallurgy is limited to PTFE, PFA, PVDF, and quartz; stainless steel, aluminium, titanium, and copper-containing alloys are incompatible. Exhaust ducting should be coated and leak-checked because hydrogen chloride vapour migrates and corrodes unlined steel. The H2O2 component may be stabilised with trace inorganic additives depending on supplier; for front-end processes, the stabilizer identity and concentration must be disclosed on the certificate of analysis because phosphorus-containing stabilizers can affect photoresist adhesion on subsequent layers. Personnel exposure limits are set by hydrochloric acid and hydrogen peroxide workplace standards; local ventilation should maintain airborne HCl below 1 ppm or the applicable occupational exposure limit. Spent working baths are drained through acid waste systems after peroxide quench and neutralisation, with metal content reported for waste discharge permits.
