Organosilicon Intermediate · Silylating Agent
Hexamethyldisilazane (HMDS)
(Bis(trimethylsilyl)amine / HMDS Anhydrous)
| CAS No. | 999-97-3 |
| IUPAC Name | 1,1,1,3,3,3-hexamethyldisilazane |
| Synonyms | HMDS, hexa methyl disilazane, 1,1,1,3,3,3-hexamethyldisilazane, bis(trimethylsilyl)amine, hexamethylsilazane, N-(trimethylsilyl)trimethylsilylamine |
| Molecular Formula | C₆H₁₉NSi₂ [(CH₃)₃Si–NH–Si(CH₃)₃] |
| Molecular Weight | 161.39 g/mol |
| HS Code | 2931900090 |
| Grade Available | Industrial Pharmaceutical Electronic (5N / 6N) |
What Is Hexamethyldisilazane (HMDS)? An Overview
Hexamethyldisilazane (HMDS), also written as hexa methyl disilazane or 1,1,1,3,3,3-hexamethyldisilazane (CAS 999-97-3), is a colorless, highly volatile organosilicon compound with a characteristic ammonia-like odor. HMDS full form: Hexamethyldisilazane - a name that reflects its structure of two trimethylsilyl groups bridged by a nitrogen atom: (CH₃)₃Si–NH–Si(CH₃)₃. This unique disilazane architecture enables efficient silylation of protic functional groups (hydroxyl, amino, carboxyl) and outstanding surface hydrophobization, making HMDS an irreplaceable chemical reagent across semiconductor lithography, pharmaceutical synthesis, advanced materials, and surface treatment industries.
Unlike traditional silylating agents such as trimethylchlorosilane (TMCS), HMDS offers milder reaction conditions, higher silylation yield, and significantly lower by-product generation - critical advantages for high-end manufacturing where strict purity and process cleanliness are required. HMDS reacts rapidly with moisture to release ammonia, so all grades must be handled and stored under nitrogen protection.
We partner with leading Chinese manufacturers - including facilities certified by SMIC and Yangtze Memory - to supply Industrial, Pharmaceutical, and Electronic Grade HMDS at competitive prices, with flexible packaging from gram-level reagent drums to industrial IBC totes, serving buyers in Europe, North America, Southeast Asia, and the Middle East.
Physical & Chemical Properties of HMDS
HMDS Specifications - All Grades
| Specification | Industrial Grade Surface Treatment / Fillers |
Pharmaceutical Grade Drug Synthesis (GMP) |
Electronic Grade Semiconductor Lithography |
|---|---|---|---|
| Purity (GC) | ≥ 98.0% | ≥ 99.5% | ≥ 99.999% (5N) up to 6N for advanced nodes |
| Water Content | ≤ 0.1% | ≤ 0.02% | ≤ 0.005% (≤ 50 ppm) |
| Color (Pt-Co) | ≤ 30 | ≤ 10 | ≤ 5 |
| Boiling Point | 125–127 °C | 126.0–126.5 °C | 126.2 ± 0.2 °C |
| Flash Point | 17 °C (closed cup) | 17 °C (closed cup) | 17 °C (closed cup) |
| Metal Impurities | Not specified | Single ion ≤ 10 ppm | Single ion ≤ 1 ppb (ppt level for 14nm nodes) |
| Shelf Life | 6 months (N₂-sealed) | 12 months (N₂-sealed, dark) | 18 months (ultra-clean N₂-sealed) |
| Packaging | 180 kg steel drum 1000 kg IBC tote |
20L HDPE drum 200L N₂-sealed steel drum |
10L quartz-lined drum 200L ultra-clean steel drum |
Complies with GB/T 30301-2013, REACH & TSCA. COA, SDS/MSDS, and third-party test reports available on request.
HMDS Uses & Application Fields
1. Semiconductor Lithography - Photoresist Adhesion Promoter
HMDS is the industry-standard adhesion promoter, primer, and hydrophobic coating agent in silicon wafer lithography, accounting for over 40% of total HMDS consumption. Applied as a vapor-phase primer (VPP) prior to photoresist coating, HMDS reacts with surface hydroxyl groups (Si–OH) on the wafer to form a dense hydrophobic trimethylsilyl layer. This dramatically improves photoresist adhesion, prevents resist peeling during development, and eliminates edge bead formation - ensuring accurate fine circuit patterning down to 28nm nodes and below.
As advanced semiconductor nodes progress to 14nm, 7nm, and beyond, purity requirements have escalated to 5N (99.999%) and 6N grades, with metal impurities controlled at the ppb–ppt level. Our electronic-grade HMDS products employ advanced trace metal removal technology, meeting the qualification standards of leading fabs including SMIC, Yangtze Memory, Changxin Memory, and UMC.
Reference: SEMI Standards - Semiconductor Materials Purity ↗
2. Pharmaceutical Industry - Silylating Agent for Drug Synthesis
In pharmaceutical synthesis, HMDS is widely used as a silylating agent to protect reactive protic functional groups (–OH, –NH₂, –COOH) in drug intermediates, preventing unwanted side reactions and significantly improving reaction selectivity and target product yield. It is a key reagent in the synthesis of anti-tumor, antiviral, and antiallergic active pharmaceutical ingredients (APIs).
Our pharmaceutical-grade HMDS (≥99.5% purity, GMP-compatible) has been validated by leading pharmaceutical CDMO enterprises and provides stable batch quality essential for drug R&D and large-scale manufacturing.
Reference: United States Pharmacopeia (USP) ↗
3. Materials & Surface Treatment - Hydrophobization Agent
HMDS is a highly effective hydrophobization agent for inorganic fillers such as fumed silica and titanium dioxide. Surface modification with HMDS significantly improves filler–matrix compatibility in silicone rubber and epoxy resin composites, enhancing mechanical properties (toughness, tensile strength) and weather resistance. It is widely used in OLED encapsulation materials and photovoltaic module glass treatment, where HMDS-modified surfaces show markedly improved moisture barrier performance, extending service life in harsh outdoor environments.
For glass, ceramic, and metal surface treatment, HMDS forms a dense, covalently bonded hydrophobic film that prevents moisture absorption and corrosion.
Reference: PubChem - Hexamethyldisilazane (NIH) ↗
4. Analytical Chemistry & Fine Chemicals
In analytical chemistry, HMDS is used as a derivatization reagent for GC analysis of protic compounds (alcohols, phenols, carboxylic acids). Silylated derivatives exhibit higher volatility and improved chromatographic separation, enabling precise quantitative analysis of trace substances in complex matrices.
In fine chemicals, HMDS serves as an intermediate for high-end silicone surfactants and silicone resins used in daily chemicals and textile printing. The electronic-grade HMDS market is projected to grow at a CAGR of 18.3% through 2026, driven by accelerating semiconductor localization and expansion of pharmaceutical CDMO capacity.
Reference: ECHA REACH Registration - HMDS ↗
5. HMDS as a Base - LiHMDS, NaHMDS & KHMDS
Beyond its role as a silylating agent, HMDS is a key precursor to the widely used metal amide bases: LiHMDS (lithium hexamethyldisilazide, lithium bis(trimethylsilyl)amide), NaHMDS (sodium hexamethyldisilazide), and KHMDS (potassium hexamethyldisilazide). These strong, hindered bases are essential reagents in pharmaceutical and fine chemical synthesis for selective enolate formation, directed deprotonation, and asymmetric reactions where steric bulk and chemoselectivity are critical.
LiHMDS (CAS 4039-32-1) is the most widely used, prized for its high basicity (pKa ~30 in THF) and excellent solubility in ethereal solvents. NaHMDS and KHMDS offer increasing reactivity and are used where LiHMDS is insufficiently reactive. All three are manufactured from HMDS as the key starting material, making high-purity HMDS supply critical to their production.
We supply high-purity HMDS suitable as feedstock for LiHMDS, NaHMDS, and KHMDS production. Contact us for bulk specifications.
How Is HMDS Made? Manufacturing Process
HMDS is manufactured commercially via two primary routes. The traditional chlorosilane ammonolysis process reacts trimethylchlorosilane (TMCS) with excess ammonia: 2 (CH₃)₃SiCl + NH₃ → (CH₃)₃Si–NH–Si(CH₃)₃ + 2 HCl. The by-product HCl is neutralized and the crude product purified by multi-stage rectification. An alternative green transamination technology uses hexamethyldisiloxane (HMDSO) and ammonia under catalytic conditions, reducing chloride by-products and environmental impact.
Our partner manufacturers operate continuous ammonolysis production lines with multi-stage rectification and molecular sieve adsorption purification systems, delivering consistent purity from batch to batch across all grades.
HMDS Storage, Stability & Safety Handling
Storage Requirements
Store in a cool (0–25°C), dry, well-ventilated explosion-proof warehouse away from heat sources, open flames, and direct sunlight. All packaging must be nitrogen-sealed to isolate moisture and air - HMDS hydrolyzes rapidly on contact with ambient humidity. Industrial grade: nitrogen-sealed steel drums. Pharmaceutical and Electronic grades: ultra-clean nitrogen-sealed HDPE or quartz-lined drums (ISO 14644 clean packaging for electronic grade). Segregate from oxidizers and strong acids with a minimum 20-foot separation or a 30-minute fire-rated barrier. Maximum stack: 2 layers for 180 kg steel drums. Equip warehouse with explosion-proof lighting and dry-powder or CO₂ fire extinguishers.
Stability Note
HMDS is chemically stable when stored dry and under nitrogen. Exposure to moisture causes hydrolysis; exposure to strong acids or oxidizers may cause violent reactions. Avoid prolonged exposure to temperatures above 30°C to prevent accelerated volatilization.
Safety & Handling (SDS / MSDS Summary)
PPE required: Anti-static clothing, nitrile rubber gloves (triple-layer for high-risk operations), chemical safety goggles, face shield, and organic vapor respirator (SCBA for confined spaces). No eating, drinking, or smoking during operations.
Spill response: Immediately cut ignition sources, evacuate upwind. Isolate spill area. Absorb with dry sand or soda ash - do NOT use water. Transfer absorbed material to sealed containers for disposal. Do not discharge to sewers or soil.
First aid: Skin - remove contaminated clothing, wash with soap and water for ≥15 min. Eyes - flush with water for ≥15 min, seek medical attention. Inhalation - move to fresh air immediately. Ingestion - do not induce vomiting; seek emergency medical care. Full SDS/MSDS PDF available from our sales team.
HMDS Price - 2025 Market Reference
The HMDS price (hexamethyldisilazane price) varies significantly by purity grade, packaging specification, and order volume. The following are indicative 2025 reference prices for China-origin product (ex-works basis):
≥ 98.0%
≥ 99.5%
≥ 99.999% (5N)
Frequently Asked Questions about HMDS
Q: What does HMDS stand for? What is HMDS full form?
HMDS stands for Hexamethyldisilazane - the full chemical name is 1,1,1,3,3,3-hexamethyldisilazane, also written as hexa methyl disilazane. In chemistry, HMDS specifically refers to this organosilicon compound (CAS 999-97-3) with the structure (CH₃)₃Si–NH–Si(CH₃)₃. Note: "HMDS" is also used as an abbreviation in unrelated fields (e.g., medical, military, or agricultural contexts), but in chemistry and semiconductor manufacturing contexts, HMDS invariably means hexamethyldisilazane.
Q: What is HMDS used for in semiconductor manufacturing?
HMDS is used as a vapor-phase adhesion promoter (primer) applied to silicon wafer surfaces before photoresist coating. It reacts with surface Si–OH groups to form a hydrophobic trimethylsilyl monolayer, which dramatically improves photoresist adhesion, prevents delamination during wet development, and ensures dimensional accuracy of fine circuit patterns. It is a standard process material at virtually every silicon wafer fab globally, from legacy 200mm to leading-edge 300mm EUV lithography lines.
Q: What is the difference between Industrial Grade and Electronic Grade HMDS?
Industrial Grade (≥98.0%) is suitable for surface treatment of fillers (fumed silica, TiO₂), coatings, and general silylation applications where trace metal content is not critical. Electronic Grade (≥99.999%, 5N) requires individual metal impurities below 1 ppb - mandatory for semiconductor lithography where sub-ppb metallic contamination would cause device failures. Electronic Grade is packaged under ultra-clean ISO 14644 conditions in quartz-lined or certified ultra-clean steel drums, with each batch accompanied by a full ICP-MS trace metals report.
Q: Why does HMDS react with water, and how should it be stored?
HMDS contains a Si–N–Si bond that is highly susceptible to hydrolysis: (CH₃)₃Si–NH–Si(CH₃)₃ + H₂O → 2 (CH₃)₃SiOH + NH₃. The released ammonia creates pressure buildup in sealed containers, and the resulting hexamethyldisiloxane (HMDSO) contaminates the product. All grades must therefore be stored under dry nitrogen in sealed containers, at 0–25°C, away from any moisture source. Open containers should be immediately re-sealed and blanketed with nitrogen after each use.
Q: What is HMDS and how does it differ from HMDSO?
HMDS (hexamethyldisilazane, CAS 999-97-3) contains a Si–N–Si linkage and is the active silylating reagent. HMDSO (hexamethyldisiloxane, CAS 107-46-0) contains a Si–O–Si linkage and is the hydrolysis by-product of HMDS - it is far less reactive. HMDS is used as a chemical surface modifier and silylation reagent; HMDSO is used mainly as a non-reactive silicone fluid and raw material for HMDS synthesis. The two should not be confused when specifying materials for lithography or pharmaceutical processes.
Q: What certifications should I require from an HMDS supplier?
For industrial applications: ISO 9001 (quality management) and ISO 14001 (environmental). For pharmaceutical grade: GMP compliance, ability to provide USP/EP-referenced COA, and third-party QC reports. For electronic grade: confirmation of downstream semiconductor fab qualification (e.g., SMIC, UMC certifications), SEMI F47 or equivalent materials standards compliance, full ICP-MS trace metals report per batch, and ISO 14644-certified clean packaging. All grades should carry current REACH and TSCA registrations for international export.
Q: What happens when HMDS reacts with water?
HMDS reacts rapidly with water via hydrolysis: (CH₃)₃Si–NH–Si(CH₃)₃ + H₂O → 2 (CH₃)₃SiOH → (CH₃)₃Si–O–Si(CH₃)₃ + NH₃. The products are hexamethyldisiloxane (HMDSO) and ammonia. This reaction is exothermic and generates ammonia gas, which creates pressure in sealed containers and degrades product purity. This is why all HMDS grades - including industrial - must be stored and handled under dry nitrogen at all times. Even ambient humidity can initiate slow hydrolysis over extended storage periods.
Q: What are the main alternatives to HMDS, and when is HMDS preferred?
Common silylating agent alternatives include trimethylchlorosilane (TMCS), N-methyl-N-trimethylsilylacetamide (MSA), and N,O-bis(trimethylsilyl)acetamide (BSA). HMDS is preferred when mild reaction conditions are required (no HCl by-product), when high silylation yield is critical, or when the process requires minimal contamination from acidic or corrosive by-products - making it the standard choice for semiconductor wafer treatment and pharmaceutical synthesis. For bulk industrial hydrophobization where cost is the primary driver, TMCS may be used as a lower-cost alternative.
Industry References & Standards
Comprehensive physicochemical properties, toxicology data, GHS classifications, and regulatory information.
International standards body for semiconductor materials purity specifications and qualification protocols.
Official EU REACH dossier: hazard classifications, exposure scenarios, and regulatory status.
Global authority for analytical and high-purity reagents; reference standard for HMDS quality benchmarking.
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We supply Industrial, Pharmaceutical, and Electronic Grade HMDS (CAS 999-97-3) with competitive pricing and flexible packaging. Contact our team for a tailored quote, SDS/MSDS, or application guidance.
Related products: Trimethylchlorosilane (TMCS) · Hexamethyldisiloxane (HMDSO) · Other Organosilicon Intermediates
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