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Step 05 Metallization / Anneal

Forming Gas Anneal Furnace

Lindberg / Tempress Systems HIGH ● Hydrogen passivation of dangling bonds reduces waveguide absorption loss

Role in QLT Fabrication

The forming gas anneal (FGA) is the final thermal step in QLT's post-metallization process, performed at 425°C for 90 minutes in a 95:5 N₂/H₂ atmosphere. This anneal is specifically referenced in the GAP01 patent specification as critical for achieving ultra-low waveguide loss: hydrogen atoms from the forming gas diffuse into the Si₃N₄/SiO₂ film stack, passivating dangling silicon and nitrogen bonds at interfaces that would otherwise act as optical absorption centers.

In silicon photonics, dangling bonds at dielectric interfaces are the dominant source of mid-gap absorption states. Each unpassivated Si≡ or ≡N bond creates a localized electronic state that absorbs photons in the near-infrared telecom band (1300–1600 nm). For quantum-grade photonic circuits operating at the single-photon level, even 0.01 dB/cm of excess absorption is significant — it directly reduces photon survival probability and degrades quantum interference visibility.

The forming gas anneal serves multiple critical functions:

  • Dangling bond passivation ● H₂ molecules dissociate at 400–450°C; atomic H diffuses to Si₃N₄/SiO₂ interfaces and terminates dangling bonds as Si-H and N-H
  • Contact resistance reduction ● anneals Ti/Au and TiN metallization contacts, forming low-resistance ohmic interfaces to waveguide heaters
  • Film stress relaxation ● relieves residual stress in PECVD SiO₂ cladding and sputtered TiN heater films
  • Defect annealing ● heals point defects in SiO₂ introduced during plasma processing (RIE, PECVD)
  • Optical loss reduction ● target: reduce waveguide propagation loss by 0.05–0.2 dB/cm through interface passivation

Why Forming Gas (Not Pure N₂ or H₂)

AtmosphereTemperaturePassivationSafetyUse Case
95:5 N₂/H₂ (our method)400–450°CExcellentNon-flammable (< LEL)Standard FGA; safe for open-tube furnaces
90:10 N₂/H₂400–450°CExcellentNon-flammable (< LEL)Faster passivation; slightly higher H₂ concentration
Pure N₂400–450°CNone (no hydrogen)InertStress relief only; no dangling bond passivation
Pure H₂400–450°CMaximumExplosive (LEL 4%)Requires sealed furnace with H₂ safety systems
N₂/D₂ (deuterium)400–450°CExcellentNon-flammable (< LEL)Shifts Si-D absorption away from telecom band

Anneal Requirements for QLT

ParameterTargetToleranceMeasurement
Temperature425°C± 5°CType-K thermocouple / profile wafer
Duration90 minutes (soak at temperature)± 5 minProcess timer
Atmosphere95:5 N₂/H₂ (forming gas)H₂ content 3–10%Gas flow ratio (MFCs)
Ramp rate (up)5–10°C/min≤ 15°C/minController ramp profile
Ramp rate (down)Natural cool (< 5°C/min)Controller readback
Temperature uniformity± 3°C across hot zone± 5°CMulti-point thermocouple survey
Gas flow rate2–5 SLM total± 10%Mass flow controller
O₂ contamination< 10 ppm during anneal< 100 ppmInline O₂ analyzer
Post-anneal loss improvement0.05–0.2 dB/cm reductionMeasurable improvementWaveguide cutback / ring resonator Q

Hydrogen Passivation Physics

FORMING GAS ANNEAL — PASSIVATION MECHANISM:

STEP 1: H₂ Dissociation (surface catalysis at 400–450°C)
H₂ → 2H• (at Si or metal surfaces)

STEP 2: Diffusion (atomic hydrogen migrates through SiO₂)
D_H(425°C) ≈ 10⁻¹⁰ cm²/s in thermal SiO₂
Diffusion length in 90 min: √(D·t) ≈ 2.3 μm
This exceeds our 1.5 μm SiO₂ cladding → H reaches Si₃N₄ interface

STEP 3: Bond Termination
Si≡ (dangling) + H• → Si-H (passivated)
≡N (dangling) + H• → N-H (passivated)

DEFECT DENSITY REDUCTION:
├── Pre-anneal interface state density: D_it ~ 10¹² cm⁻²eV⁻¹
├── Post-anneal interface state density: D_it ~ 10¹⁰ cm⁻²eV⁻¹
├── Improvement: 100× reduction in absorbing states
└── Optical impact: 0.05–0.2 dB/cm loss reduction at 1550 nm

TEMPERATURE CONSTRAINTS:
├── Minimum: 350°C (insufficient H₂ dissociation below this)
├── Optimum: 400–450°C (maximum passivation efficiency)
├── Maximum: 500°C (beyond this, H can desorb from Si-H bonds)
├── As₂S₃ constraint: T_g = 200°C → FGA must precede As₂S₃ deposition
├── PVDF constraint: T_g = 130°C → FGA must precede PVDF deposition
└── TiN heaters: stable to 600°C → no concern

N-H ABSORPTION WARNING:
├── Si-N-H bonds absorb at ~1520 nm (near telecom C-band edge)
├── This is normally a concern for LPCVD Si₃N₄ films
├── QLT Si₃N₄ is pre-annealed at 1100°C by MPW foundry
│   └── High-T anneal drives out bulk N-H; FGA only adds interface H
├── Interface N-H density is 100–1000× lower than bulk
└── Net effect: absorption reduction far exceeds any N-H addition

Technical Specifications

Lindberg/Blue M Horizontal Tube Furnace

ParameterSpecification
ManufacturerLindberg/Blue M (Thermo Fisher Scientific)
ModelHTF55000 Series (3-zone horizontal tube furnace)
Websitethermofisher.com
Tube diameter3" or 4" (76 mm or 100 mm) fused quartz
Hot zone length24" (610 mm) — 3-zone independent control
Temperature range100–1200°C
Temperature uniformity± 3°C across center 18" at 425°C
Heating elementsKanthal A-1 wire (Fe-Cr-Al) embedded in ceramic fiber
Ramp rateUp to 20°C/min (empty); 5–10°C/min typical with load
ControllerEurotherm 3504 (PID, ramp/soak programming, RS-485)
Wafer capacity4" tube: up to 150 mm wafers in quartz boat (4–25 wafers)
Gas handlingEnd-cap with gas inlet/outlet; MFC-controlled
ExhaustBubbler (oil or DI water) for positive pressure indication
SafetyOver-temperature protection; thermocouple break protection

Tempress Systems Horizontal Diffusion Furnace

ParameterSpecification
ManufacturerTempress Systems (Vaassen, Netherlands)
ModelTS Series 8000 (horizontal diffusion/anneal furnace)
Websitetempress.nl
ConfigurationHorizontal, 4-stack (up to 4 independent tubes)
Tube diameterUp to 200 mm (8") process tube
Temperature range200–1200°C (3 or 5 zone heating)
Temperature uniformity± 1°C across flat zone (production grade)
Wafer capacityUp to 200 mm wafers; 25–50 wafer batch
Gas panelIntegrated MFC manifold; N₂, forming gas, O₂ lines
AutomationSemi-auto or full-auto wafer loading (cantilevered paddle)
ControlPC-based SCADA with recipe management and data logging
ComplianceSEMI S2/S8; CE marked

Process Integration

QLT PROCESS FLOW ● Forming Gas Anneal (Step B9 — Post-Metallization):

PRE-REQUISITES:
├── All metallization complete (TiN heaters + Ti/Au contact pads)
├── PECVD SiO₂ top cladding deposited (Step B8)
├── Via openings etched through SiO₂ to Au pads (if applicable)
├── All photoresist stripped; wafer clean
└── NO temperature-sensitive materials yet deposited
    ├── As₂S₃ overlay: NOT YET (T_g = 200°C)
    ├── PVDF-TrFE: NOT YET (T_g = 130°C)
    └── Polymer adhesives: NOT YET

STEP 1: Furnace Preparation
├── Set furnace to 425°C (allow 1–2 hr stabilization)
├── Purge tube with N₂ at 5 SLM for 15 min
│   └── Displaces residual O₂; prevents oxidation during anneal
├── Verify temperature profile: ± 3°C across hot zone
└── Verify O₂ level < 10 ppm (inline analyzer or gettered gas)

STEP 2: Wafer Loading
├── Load wafer(s) into quartz boat (source end of tube)
├── Slow-push into hot zone (2–3 cm/min) under N₂ flow
│   └── Prevents thermal shock; gradual ramp from 200→425°C
├── Position wafers in center of flat zone
└── Wait 5 min for temperature equilibration

STEP 3: Forming Gas Anneal
├── Switch gas from pure N₂ to 95:5 N₂/H₂ forming gas
├── Flow rate: 3 SLM through process tube
├── Soak time: 90 minutes at 425°C
├── Monitor gas bubbler (positive pressure indication)
└── Log temperature and gas flow throughout anneal

STEP 4: Cool-Down
├── Switch back to pure N₂ (3 SLM)
├── Slow-pull wafer boat out of hot zone (2–3 cm/min)
├── Cool in N₂ atmosphere to < 200°C before removal
│   └── Prevents oxidation of freshly passivated surfaces
├── Total cool-down: 30–60 min (natural, no forced air)
└── Remove wafer; store in N₂ desiccator

STEP 5: Post-Anneal Verification
├── Measure TiN heater resistance (expect 5–15% decrease from anneal)
├── Visual inspection: no discoloration, no peeling
├── Optional: waveguide loss measurement (ring resonator Q)
│   └── Compare pre-anneal vs post-anneal Q factor
├── Contact resistance measurement (TLM structures if available)
└── Proceed to As₂S₃ overlay deposition (if applicable)

PROCESS WINDOW:
├── Temperature: 400–450°C (optimum 425°C)
├── Time: 30–120 min (optimum 90 min; diminishing returns beyond)
├── Below 400°C: insufficient H₂ dissociation
├── Above 450°C: risk of H desorption from weak bonds
└── Above 500°C: TiN oxidation risk if O₂ contamination present

Vendor Options & Pricing

New System Pricing

ModelManufacturerConfigurationPrice (2025–2026)Lead Time
Lindberg/Blue M HTF55000Thermo Fisher (USA)3-zone, 4" tube, 1200°C$15,000–$35,000 (furnace only)4–8 weeks
Tempress TS 8000Tempress (Netherlands)4-stack, 200 mm, automated$500,000–$1,000,00016–24 weeks
Centrotherm c.FURNACECentrotherm (Germany)Vertical, 200 mm, batch$400,000–$800,00014–20 weeks
Tystar TitanTystar Corp (CA)Horizontal, 200 mm, 4-tube$300,000–$600,00012–18 weeks
MRL Industries 1100MRL Industries (CA)3-zone, 4–6" tube$20,000–$50,0006–10 weeks

Refurbished Market

ModelConditionPriceLead TimeSource
Lindberg/Blue M 3-zone tubeRefurbished, new elements$5,000–$15,0002–4 weeksLabX, Thermo resellers
Tempress / Bruce diffusion furnaceRefurbished, 4-stack$30,000–$80,0004–8 weeksCapovani, ClassOne
Tystar Titan IIRefurbished$40,000–$100,0004–8 weeksSemiStar, CAE
Thermco / SVG tube furnaceAs-is / refurbished$8,000–$25,0002–4 weeksFabSurplus, Machinio
Centrotherm verticalRefurbished$50,000–$150,0006–10 weeksUsed-Line, CAE

Facility Requirements

Space and Utilities

ParameterSpecification
PowerSingle-phase 240V, 30A (benchtop Lindberg: 3–8 kW); 3-phase 208V, 60A (production Tempress)
Forming gas (95:5 N₂/H₂)Standard cylinder with dual-stage regulator; ~$100–$200/cylinder
N₂ purge gasHouse N₂ or LN₂ dewar; UHP (99.999%) recommended
Exhaust4" duct to fume hood or building exhaust (H₂ below LEL — not classified flammable)
Quartz process tube3–4" diameter × 36–48" long; $500–$1,500 replacement
Quartz wafer boatHolds 4–25 wafers; $200–$500
Floor space1.0 m × 0.6 m (benchtop); 2.0 m × 1.5 m (production stack)
Weight50–100 kg (benchtop); 500–2000 kg (production)
VibrationNot sensitive
Temperature ambientStandard lab 18–28°C; furnace radiates significant heat

Safety & Handling

Hazard Summary

HazardSourceRisk LevelControls
Burn hazard425°C furnace tube and exterior surfacesHIGHThermal shields; warning labels; heat-resistant gloves; cool-down SOP
H₂ accumulationForming gas leak in enclosed spaceLOW (5% H₂ is below 4% LEL in air)Room ventilation; no ignition sources near exhaust; H₂ sensor optional
Quartz tube breakageThermal shock; mechanical stressLOWSlow ramp rates; careful handling; safety shields on tube ends
Asphyxiation (N₂)Large N₂ flow in enclosed areaLOWO₂ monitor in room; adequate ventilation (> 6 ACH)
ElectricalHeating element power (3–8 kW)LOWGrounded enclosure; GFCI protection; lockout/tagout for maintenance

Forming Gas Safety Notes

FORMING GAS (95:5 N₂/H₂) SAFETY:

CLASSIFICATION: NON-FLAMMABLE mixture
├── H₂ content (5%) is BELOW the Lower Explosive Limit (LEL = 4% in air)
├── Even a 100% release of forming gas into air will not reach LEL
├── Standard compressed gas cylinder handling applies
├── No flammable gas cabinet required
└── No H₂ sensor legally required (but recommended for best practice)

COMPARISON TO PURE H₂:
├── Pure H₂: LEL 4%, UEL 75%, autoignition 500°C → EXTREMELY FLAMMABLE
├── 95:5 forming gas: even undiluted, H₂ is only 5% → cannot reach LEL
├── At furnace exhaust: further diluted by room air → effectively zero risk
└── This is why forming gas is the standard industry choice for FGA

CYLINDER HANDLING:
├── Secured to wall or bench with chain/strap
├── Regulator: CGA-580 (inert gas) fitting
├── Flow: 2–5 SLM through process tube
├── Consumption: ~1 cylinder per 10–20 anneals (K-size)
├── Cost: $80–$150 per cylinder
└── Storage: standard compressed gas area; no special ventilation
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